It's as easy as putting units in in fact it's quite the same until you come to the CLsystem. (How to simply add a building should be plenty of info in the forum it's just the Lsystem that is a bit tricky).
You basically use these files:
CIV4ArtDefines_Building.xml
example:
<BuildingArtInfo>
<Type>
ART_DEF_BUILDING_ACADEMY</Type>
<bAnimated>0</bAnimated>
<fScale>0.9</fScale>
<fInterfaceScale>1.5</fInterfaceScale>
<NIF>Art/Structures/Buildings/Academy/Academy.nif</NIF>
<KFM/>
<Button>,Art/Interface/Buttons/Buildings/Academy.dds,Art/Interface/Buttons/Buildings_Atlas.dds,7,11</Button>
</BuildingArtInfo>
CIV4BuildingClassInfos.xml
<BuildingClassInfo>
<Type>
BUILDINGCLASS_ACADEMY</Type>
<Description>TXT_KEY_BUILDING_ACADEMY</Description>
<iMaxGlobalInstances>-1</iMaxGlobalInstances>
<iMaxTeamInstances>-1</iMaxTeamInstances>
<iMaxPlayerInstances>-1</iMaxPlayerInstances>
<iExtraPlayerInstances>0</iExtraPlayerInstances>
<bNoLimit>0</bNoLimit>
<bMonument>0</bMonument>
<DefaultBuilding>
BUILDING_ACADEMY</DefaultBuilding>
<VictoryThresholds/>
</BuildingClassInfo>
CIV4BuildingInfos.xml
<BuildingInfo>
<BuildingClass>
BUILDINGCLASS_ACADEMY</BuildingClass>
<Type>
BUILDING_ACADEMY</Type>
<SpecialBuildingType>NONE</SpecialBuildingType>
<Description>TXT_KEY_BUILDING_ACADEMY</Description>
<Civilopedia>TXT_KEY_BUILDING_ACADEMY_PEDIA</Civilopedia>
<Strategy>TXT_KEY_BUILDING_ACADEMY_STRATEGY</Strategy>
<Advisor>ADVISOR_SCIENCE</Advisor>
<ArtDefineTag>ART_DEF_BUILDING_ACADEMY</ArtDefineTag>
<MovieDefineTag>NONE</MovieDefineTag>
<HolyCity>NONE</HolyCity>
<ReligionType>NONE</ReligionType>
<StateReligion>NONE</StateReligion>
<PrereqReligion>NONE</PrereqReligion>
<GlobalReligionCommerce>NONE</GlobalReligionCommerce>
<VictoryPrereq>NONE</VictoryPrereq>
<FreeStartEra>NONE</FreeStartEra>
<MaxStartEra>NONE</MaxStartEra>
<ObsoleteTech>NONE</ObsoleteTech>
<PrereqTech>NONE</PrereqTech>
<TechTypes/>
<Bonus>NONE</Bonus>
<PrereqBonuses/>
<ProductionTraits/>
<HappinessTraits/>
<PowerBonus>NONE</PowerBonus>
<FreeBonus>NONE</FreeBonus>
<iNumFreeBonuses>0</iNumFreeBonuses>
<FreeBuilding>NONE</FreeBuilding>
<FreePromotion>NONE</FreePromotion>
<CivicOption>NONE</CivicOption>
<GreatPeopleUnitClass>NONE</GreatPeopleUnitClass>
<iGreatPeopleRateChange>0</iGreatPeopleRateChange>
<iHurryAngerModifier>0</iHurryAngerModifier>
<bBorderObstacle>0</bBorderObstacle>
<bTeamShare>0</bTeamShare>
<bWater>0</bWater>
<bRiver>0</bRiver>
<bPower>0</bPower>
<bDirtyPower>0</bDirtyPower>
<bAreaCleanPower>0</bAreaCleanPower>
<bDiploVote>0</bDiploVote>
<bForceTeamVoteEligible>0</bForceTeamVoteEligible>
<bCapital>0</bCapital>
<bGovernmentCenter>0</bGovernmentCenter>
<bGoldenAge>0</bGoldenAge>
<bMapCentering>0</bMapCentering>
<bNoUnhappiness>0</bNoUnhappiness>
<bNoUnhealthyPopulation>0</bNoUnhealthyPopulation>
<bBuildingOnlyHealthy>0</bBuildingOnlyHealthy>
<bNeverCapture>0</bNeverCapture>
<bNukeImmune>0</bNukeImmune>
<bPrereqReligion>0</bPrereqReligion>
<bCenterInCity>0</bCenterInCity>
<iAIWeight>0</iAIWeight>
<iCost>-1</iCost>
<iHurryCostModifier>0</iHurryCostModifier>
<iMinAreaSize>-1</iMinAreaSize>
<iConquestProb>100</iConquestProb>
<iCitiesPrereq>0</iCitiesPrereq>
<iTeamsPrereq>0</iTeamsPrereq>
<iLevelPrereq>0</iLevelPrereq>
<iMinLatitude>0</iMinLatitude>
<iMaxLatitude>90</iMaxLatitude>
<iGreatPeopleRateModifier>0</iGreatPeopleRateModifier>
<iGreatGeneralRateModifier>0</iGreatGeneralRateModifier>
<iDomesticGreatGeneralRateModifier>0</iDomesticGreatGeneralRateModifier>
<iGlobalGreatPeopleRateModifier>0</iGlobalGreatPeopleRateModifier>
<iAnarchyModifier>0</iAnarchyModifier>
<iGlobalHurryModifier>0</iGlobalHurryModifier>
<iExperience>0</iExperience>
<iGlobalExperience>0</iGlobalExperience>
<iFoodKept>0</iFoodKept>
<iAirlift>0</iAirlift>
<iAirModifier>0</iAirModifier>
<iNukeModifier>0</iNukeModifier>
<iNukeExplosionRand>0</iNukeExplosionRand>
<iFreeSpecialist>0</iFreeSpecialist>
<iAreaFreeSpecialist>0</iAreaFreeSpecialist>
<iGlobalFreeSpecialist>0</iGlobalFreeSpecialist>
<iMaintenanceModifier>0</iMaintenanceModifier>
<iWarWearinessModifier>0</iWarWearinessModifier>
<iGlobalWarWearinessModifier>0</iGlobalWarWearinessModifier>
<iHealRateChange>0</iHealRateChange>
<iHealth>0</iHealth>
<iAreaHealth>0</iAreaHealth>
<iGlobalHealth>0</iGlobalHealth>
<iHappiness>0</iHappiness>
<iAreaHappiness>0</iAreaHappiness>
<iGlobalHappiness>0</iGlobalHappiness>
<iStateReligionHappiness>0</iStateReligionHappiness>
<iWorkerSpeedModifier>0</iWorkerSpeedModifier>
<iMilitaryProductionModifier>0</iMilitaryProductionModifier>
<iSpaceProductionModifier>0</iSpaceProductionModifier>
<iGlobalSpaceProductionModifier>0</iGlobalSpaceProductionModifier>
<iTradeRoutes>0</iTradeRoutes>
<iCoastalTradeRoutes>0</iCoastalTradeRoutes>
<iGlobalTradeRoutes>0</iGlobalTradeRoutes>
<iTradeRouteModifier>0</iTradeRouteModifier>
<iGlobalPopulationChange>0</iGlobalPopulationChange>
<iFreeTechs>0</iFreeTechs>
<iDefense>0</iDefense>
<iBombardDefense>0</iBombardDefense>
<iAllCityDefense>0</iAllCityDefense>
<iAsset>6</iAsset>
<iPower>0</iPower>
<fVisibilityPriority>1.0</fVisibilityPriority>
<SeaPlotYieldChanges/>
<GlobalSeaPlotYieldChanges/>
<YieldChanges/>
<CommerceChanges/>
<ObsoleteSafeCommerceChanges>
<iCommerce>0</iCommerce>
<iCommerce>0</iCommerce>
<iCommerce>4</iCommerce>
</ObsoleteSafeCommerceChanges>
<CommerceChangeDoubleTimes/>
<CommerceModifiers>
<iCommerce>0</iCommerce>
<iCommerce>50</iCommerce>
</CommerceModifiers>
<GlobalCommerceModifiers/>
<SpecialistExtraCommerces/>
<StateReligionCommerces/>
<CommerceHappinesses/>
<ReligionChanges/>
<SpecialistCounts/>
<FreeSpecialistCounts/>
<CommerceFlexibles/>
<CommerceChangeOriginalOwners>
<bCommerceChangeOriginalOwner>0</bCommerceChangeOriginalOwner>
<bCommerceChangeOriginalOwner>0</bCommerceChangeOriginalOwner>
<bCommerceChangeOriginalOwner>1</bCommerceChangeOriginalOwner>
</CommerceChangeOriginalOwners>
<ConstructSound>AS2D_BUILD_LIBRARY</ConstructSound>
<BonusHealthChanges/>
<BonusHappinessChanges/>
<BonusProductionModifiers/>
<UnitCombatFreeExperiences/>
<DomainFreeExperiences/>
<DomainProductionModifiers/>
<BuildingHappinessChanges/>
<PrereqBuildingClasses/>
<BuildingClassNeededs/>
<SpecialistYieldChanges/>
<BonusYieldModifiers/>
<Flavors>
<Flavor>
<FlavorType>FLAVOR_SCIENCE</FlavorType>
<iFlavor>10</iFlavor>
</Flavor>
</Flavors>
<HotKey/>
<bAltDown>0</bAltDown>
<bShiftDown>0</bShiftDown>
<bCtrlDown>0</bCtrlDown>
<iHotKeyPriority>0</iHotKeyPriority>
</BuildingInfo>
Have a look at those files and see how they link.
All lines that should concern you are in bold, the rest you can probably ignore for now
The tricky part Kael offered help for is this one:
CIV4CityLSystem.xml
<!-- LEAF 2x1 BUILDINGS -->
<ArtRef Name="building:BUILDING_ACADEMY">
<Attribute Class="Rotation">0,180</Attribute>
<Scale>2.0</Scale>
</ArtRef>
For now you could simply replace existing buildings with your new added ones in that file if they match in size but this won't lead to perfect results so learning more about it is obligatory on long term.