Sunwell Angratha is the best populated for PVE and PVP!
What wotlk server is the best/most populated for pve and pvp? Sunwell is the most populated right now. If you decide to start as Alliance on Angrathar, add Celes.
Probaly Sunwell's server called "Angrathar" or one of the Warmane servers (think they are called Icecrown and Lordaeron) one of them is 7x xp rates whilst the other is 1x. I know one of them (guessing the 7x) has a shop where you can buy gear, and even though like Shadowmourne is prolly insanely expensive, I do hear people say that people do buy it. If that's true or not I wouldn't know.
Angrathar has 2x XP to start with which transfers into 1x at one point, think it's 70. You can use RAF though to make it 3x instead, and I'm unsure how long that lasts (like if it's through all the levels like the XP boost you can buy from their shop, or if it stops at 70 aswell)
Then there is Gamer District, think it's mostly a german(?) server, but supposedly has really good scripting, and at least a few months ago there were lots of english speaking players starting there under the guild name of "English Please"
Other than that I do hear of Dalaran WoW, which I also think is a WoTLK server, but I could be wrong, haven't checked it out myself. But it is supposedly good aswell.
Angrathar is the server that is most "fresh" in the fact that it's the newest. Whilst at least the Warmane ones are on ICC, and I don't know about the other two.
There is also a server called "Memories" but it had a rocky start just recently, and I do believe their population and reputation has been tainted by it, but you can check it out yourself. I think they raised the xp rates because of the rocky start aswell, and they had plans with some mythic+ish dungeons and custom scripted difficulty of raids and what not, unsure how that turned out :)