I concur with the point about emailing the CEO, unless it's obvious the position would report directly to them. Best bet would be trying to find a direct line of communication via your social network (and by that I mean people you actually know, not people who follow you on Twitter, though the two may intersect).

As for the AOL addresses--well, if your address is tightjeans@aol.com (I've seen it on a resume), then, yeah, probably worth it to get a GMail address. But if it's jsmith@aol.com, I wouldn't worry much about it.