Gotta say, upon rewatching the premiere again I think I've isolated my absolute favourite moment in the episode. Surprisingly it's not a song, nor a scene of particular action or humour.
It's just that quick moment at the end when Twilight gives a relieved "Good job, Spike"
I don't know why, maybe it's the BGM or the timing or something, but it gets me right in the feels.
...
*Is mesmerised*