I'm gonna shock everyone and go with Evans' Cap.
While I loved the movie Thor and Hemsworth's performance, Evans was just straight-up more endearing. It's not really Hemsworth's fault; Thor's whole schtick in the movie is that he's a fish out of water on Earth, so he kind of stands apart from the rest of the cast and has to remain somewhat alien and awkward. Evans' Cap--scratch that, Evans' Steve Rogers--on the other hand, is eminently human and earnest in all the ways Steve should be. It's a testament to the writing and his performance that I can easily count off several great moments from his movie where Evans makes Steve shine: the fight in the alley where Steve never backs down, the scene where scrawny-ass Steve jumps on the grenade while all the buff recruits run like *****es, the scene where Steve and Dr. Erskine share a drink, etc. Like I said, I loved Thor and I thought the movie did a great job portraying some of the best aspects of his character, but he's really complex and hard to nail down in just two hours with all the other stuff the movie needed to accomplish swirling around him. Steve's much easier to establish an instant rapport with and, consequently, he came off a bit more likable, thanks in large part to Evans' selling that likability.