Here I come with my incredibly limited comic knowledge:
Wasn't Captain America not associated with the first group of Avengers? Wasn't he before their time?
During fighting Keiser(or Keizer whatever) A missile got set off and he was on it, before it exploded he jumped off it and fell into a lake. The lake froze so he was basically suspended in time, until SHIELD unfroze him, and of course put the Avengers together.