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Seeing as I am trying to get my buddy into the hobby, I am curious as to what army is the hardest to learn to play? I have the understanding that all armies are supposed to be pretty much equal but I know that can't be possible. As far as what army I think is the hardest to learn to play, I think its Dark Eldar, I might be wrong though. What do you think?

Dark Eldar, as you said, are pretty tricky. Daemons too, just because they are so different to pretty much every other army out there.

Eldar and Dark Eldar can be this. They trade in survivability for higher hitting power, so you cant make mistakes with them. Daemons dont have that much of a learning curve, but it largely depends on the dice roll for them.

Now what about space marine chapters such as Black Templars or Blood Angels, or do all space marine chapters have the same learning curve?

Vanilla marines are more shooting-focused. Everything else is basically "point and click" style of warfare (i.e: you dont ahve to worry about cover or template weapons as much as others, and given the Variant Chapter's rules and equipment, it's usually a good idea to charge into combat).

Most Marine armies have a very low learning curve. Unless you're going for a really low model count mobile force (like one centering on bikers) you shouldn't have any trouble learning. Blood Angels, Space Wolves, and Black Templars are all very punchy armies, and while they can shoot as well as regular Marines they're more close combat oriented. Each has their own quirks (Blood Angels are faster, Space Wolves are choppier and have cavalry and more heroes, Templars are more horde-centric) but they're still Marines and aren't terribly hard to play.

Guard and Orks aren't hard to play either, but you need to learn a bit of orders synergy with Guard to really get the most out of them. Either way, prepare for catastrophic casualties every game, which is just how I like it!