Avengers v.1 #197: When Iron Man steps down as team leader, Steve's afraid it's because of him.

New Avengers v.2 #2: The Avengers all thought Cap's "Rick/Bucky thing" was weird, but Tony understood. And can I just say that the Oral History of the Avengers is a brilliant thing? XD

I know you're waiting on Avengers: Prime stuff, but let me just nominate the cover of #2 while I'm thinking about it: In which staring longingly isn't enough for Tony - he can't stop himself from reaching for Steve, too. (This issue? Good lord, the subtext is barely sub. LOL.)

Avengers: The Origin, #5: When Iron Man thinks about the future, Cap's one of the first people he envisions. (Absolutely gorgeous artwork on this mini, btw.)

And more odd little things. (I'm working my way through the main series again, but I had to wander off and poke at the interesting little minis they've done, for a while. :)
Avengers Fairy Tales #1: If the Captain doesn't plan it, it's not fun.
Avengers Fairy Tales #4: The Tin Man is the one who asks the Cowardly Lion to join the journey... and when can Cap ever turn him down? (Also? This mini... beautiful, beautiful artwork.)