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I think A Friend In Deed is a great Pinkie episode too, though maybe I just think so due to it being the first episode I watched in full. Party Of One is definitely...memorable however, and another episode rotated completely around her personality. A good point for Pinkie is that, while she's often just comic relief in normal episodes, her spotlight episodes have her character pretty much carry the entire thing.
I'd say Applebuck Season is the most defining for AJ since it revolves around her personality carrying things a lot more. She was okay in Super Cider Squeezy, but a lot more stuff was working the episode in that instance, the charismatic antagonists, the other Apples, RD's cider gag. Same for the Last Roundup (how could she compete with Derpy?).
As for Spike, a tie between Owl's Well That Ends Well or Dragon Quest (though the former may get credit since it revolves around his actions a lot more, plus
Dastardly Whiplash Spike).
With that in mind, I do like a lot of duo episodes (eg. Look Before You Sleep, Fall Weather Friends) and they have similar character establishment.
edited 19th Sep '12 7:58:56 AM by Psi001