I'd watch an avengers show with this kind of cuteness and animation style. Season 1 of avengers:earths mightiest hero's was fun and kinda similar animation at times (i've not seen any recent episodes). Season 1 even had hawkeye and hulk as important characters Captain america is a hard character to do right in live action animation or comics but I think they did a great job in his movie and avengers.
Twilight's with Fury, AJ's with Capt. America, Fluttershy's with Hulk, Rainbow is obviously Iron Man, Rarity is Black Widow, but I have a hard time seeing Pinkie as Thor. Unless Pinkie is Loki, like Oki Doki Loki, and some other pony is Thor. I like it.