I think Floyd were a different band in 1967 and while Piper is the one Floyd album I'd still give a five-star rating to, I'm weirdly not that hung up on that era of the band, like live performances or bootlegs. I haven't spent much time reading up on the Syd story either. The best song from that period is "See Emily Play" which did not appear on the album anyway, and then there's the famous lost songs like "Vegatable Man," but I only like "Scream Thy Last Scream" and "Apples & Oranges," and even then only part as much as I like the best stuff on Piper.
I am a big fan of "Scarecrow" for....uh, some reason. I think it's the way it fades in with that toy organ and guitar strums, sounds beautiful with the sun going down. It might be my favorite song on the album!