Early game build order

[Spazzmaticus]

I've been playing some higher difficulties recently and experimenting with early game build orders and what I conclude is that starting with scout is mediocre. Due to the new movement system and the abundance of rough terrain, scout is only slightly faster than other units and the AIs start with so many units that you can expect to only get a few goodie huts anyway.
Hunting for tribal villages also has pretty high variance, sometimes you get lucky and get something nice, but usually it's just gold or some tech boost.

What I found best (and much more consistent than hunting for huts) is starting with:
Slinger -> Builder -> Slinger -> Slinger -> Upgrade to Archers -> take a couple city states.

No kidding.
Starting Warrior + 3 Archers can capture *any* city state. Even on Deity, I was able to capture 2 city states before the others were even close to Ancient Walls. Works best if you boost the Archery research by killing a barb with a slinger but even if not, then no big deal. You can grab both Mining and Animal Husbandry before going for archery and still have time before the 3rd slinger is ready.
The best thing about this opening is that the captured cities already have some population in them and often come with buildings and sometimes even districts.

You might think that you'd rather have them as allies, but on higher difficulties AIs really like to capture them for themselves, so this way you beat them to it.

On Emperor and below you should be able to use that little army to wipe out your closest neighbor instead. AI has no idea how to deal with archers, so you can easily shoot down any warriros/chariots they send your way and then proceed to shoot their cities to death.

Following this path nets you a few developed cities and an army sizable enough to discourage AIs to DOW you.

 

[rkade8583]

Warcarts and slingers for me and my Sumerian brothers and sisters. Start with 3 carts (1 cart, 1 builder, 2 carts) and roll out. While they're pillaging, killing barbs and such, you build slingers to back them up (and upgrade into archers.)

I faceroll the continent and then steamroll the competition. Sure I COULD go over there... but I like it over HERE!

 

[Waywocket]

I feel like if you're on deity and you spawn near Harald, you need to start slinger, slinger, warrior to have a chance. Aside from Harald, at least one slinger in your first couple of builds seems pretty important.

In Civ V I typically start scout, scout or scout, monument, but I feel like VI rewards early military units much more. First they seem to be cheaper to build, or cheaper relative to the other options - though that's just a feeling; I've not gone back and confirmed. Second it's so much easier to take (or lose!) cities with early units now that cities have no natural defences, making these units relatively more powerful. Third you have fewer buildings available so taking a time out to build units isn't a tough choice any more. And finally fourth, going wide and going violent is so much more rewarding, because there appears to be absolutely no downside to conquest, so getting an early military is more powerful.

 

[elitetroops]

I agree, opening with scout is bad. Slingers and upgrade to archers is way better. Archers can take out 1-2 AI on deity as well. When to build the builder depends on starting location.

First they seem to be cheaper to build, or cheaper relative to the other options - though that's just a feeling; I've not gone back and confirmed.

They are cheaper. No idea why, but you get 50%-100% production bonus toward all ancient and classical era units on emperor+. It doesn't kick in immediately, but a couple of dozen turns into the game. In my tests it kicked in whenever I researched Craftmanship (good reason to put an early builder in your build order), someone else found it to be more random. This is probably a bug, hope it's patched soon.

 

[toptech]

Plus I feel like scouts can't get around that much better than other units in this game. In V scouts ignored all terrain penalties, while in this build they only gain one extra movement point. This makes them better only when moving on flat land. They can't move onto two hills or forests in one turn like they could, nor can they cross rivers without full points. Might as well just build combat units that can be used for killing barbs or other players.

 

[jakedamus]

Scouts should still be the first build. Why? for boosts.
Scouts will level up pretty quickly. By two upgrades you can have improved movement through both trees and hills. You will explore much faster than a regular warrior etc. Sure on higher difficulties you won't get as 'many' huts but you still need to discover 3 city states, a natural wonder, another civ and another continent. You want to get these bonuses as early as possible so you can beeline to political philosophy, UU techs and build required districts. Slinger should be second to defend and for the archery boost. Third should be a builder for further boosts.
After those 3 builds I agree with everyone else here: build a military and cap some early civilizations!

 

[xDaunt]

For deity and immortal: scout, slinger, slinger, settler/builder, builder/settler, warrior, lots of archers (you need 6-7, including your initial slingers). From there, it kinda depends upon what you want to do.