I like the suggestion of multiple leader choices but don't think they should be divided along on arbitrary line like "evil". Just pick two sufficiently famous but different ones.
As for evil civs:
1. starting next the the huns, aztecs, iroquois, mongols, or zulu: I pretty much know war is coming and start preparing for the inevitable that moment--they always attack early.
2. starting near greece, rome, france, germany, japan, russia, spain, (maybe more?): they will almost always attack, but will be smarter about it, building up some infrastructure and waiting for you to build a few juicy wonders. They will strike sooner if you leave your military looking weak or expand quickly. I haven't had much luck derailing them. If I'm weak they attack, if I'm doing well they attack--just wait slightly longer. Basically, if you're doing better than them I've decided.
3. America, Askia, Babylon, Persia etc: Sleeper cultures. They want war but can sometimes wait forever. If you're farther away they're great friends but if you're near no amount of history is going to save you in the long run--especially if you're winning.
4. Kamehameha, Siam, Egypt (and many others) - never seen them not start wars but they like to pick on weak people and can be derailed by having common enemies even if they're nearby.
There's only a small handful of cultures I've seen not start wars as a pattern most games, but as a general rule everyone will if it looks tempting enough. Examples: India, Maya
I actually haven't been near enough or in games with everyone (also only have G&K) so I can't vouch for the rest. As a whole they seem really warlike compared to Civ IV or III though. It's like a feeding frenzy when someone gets weak, especially someone disliked.