I like to dub Sylar the cupcake-Spock mix. Exactly the kind of person Kirk wants to prove wrong and crumble. Everything about Sylar is completely and utterly dysfunctional and Kirk is somewhat surprised that Sylar can't really see it. There's a part of him, the big-heart captain part of him that's telling him to keep his options open and see if he can help. But the other, louder and less rational part just wants to fiddle with Sylar and have him get pissed off at Jim all the time, because when he does, Jim knows he's won. And Jim hinges on winning.

Basically, Jim will still ... "help" Sylar if he needed it (because it's logical! murderer aside and whatnot lol Nero) but Jim doesn't mind just fiddling around with Sylar, itching to get a strong emotional rise from the man. The fact that you're sporting Spock's look is a bonus.