There is no official editor in Civ4.
For your mod, It depends on what you want it to do.
Example : You want to add a NEW unit appearing with Horse Riding who is not HorseArcher, lets call it Horseman. 1) Find an unit graphic of a mounted warrior that don't use bow 2) follow Rabbit, White tut about adding unit keeping in mind that you are adding a new UnitClass with his default type, name, strategy, pedia entry, artdefines
Same with buildings, etc ...
You must know that you will be limited to available mechanics under the part of the game you mod. To get rid of that you will have to code new stuff at the Python or C++ Layer. And pitboss don't have anything to do with modding, methinks.