Barrowman, Victor Garber and Jesse L. Martin (Joe West) have all been in Broadway shows. I don't know if impressed is the right word, since we already knew Joe could sing from Earth-2, and I know Victor Garber can sing because I like Victor Garber and I know things.
Gustin, Benoist and the guy playing Music Meister were all on Glee together, which was heavily referenced at the end of the episode.
Winn's singing came out of nowhere. So, yes. Impressed is the right word.