Yeah, I always imagine Captain America as a seasoned veteran who's in his mid 30s. Mark Valley would've made a great Cap too but he's 10 years too old, imo. My little brother, who apparently knows more about Cap than I do, says Cap's age is around his mid-to-late 20s.
A big problem with Chris Evans being Cap is that no only will he not be able to stand on his own in his own film, but he'll be overshadowed by other actors in the Avengers movie. We have Edward Norton and Robert Downey Jr. who are both acclaimed actors playing their respective characters superbly, then we have Chris Evans who looks like he's barely out of his teens and hasn't had any serious roles (that I know of) or any acting accolades (that I know of). Captain America should not be out done by any one. And even though I've only seen Chris Hemsworth in the first 10 minutes of Star Trek, I enjoyed him tremendously. I think he'd make a good Thor. But that Alexander Skarsgård...I wouldn't mind seeing him playing Thor either.