There was a particular order I saw stuff on the series so I might as well post it here for reference's sake:
Way back in high school sometime:Episode 5 dub (on VHS) and a short scene (fansubbed) of Asuka fighting the JSSDF, I couldn't get into episode 5 because I didn't know what the plot was so I held off on watching the series for some time. (Plus I heard things about Anno being a dick and Mecha wasn't my thing.)
A few years later, in college (2005 or 06):Raw Japanese DC22' mindrape clip (I was googling for stuff on the series and stumbled across it, I think it subconsciously made me like Asuka/Shinji.
The clip sauce was Evangelion.tv), Episode 03 on Adult Swim, the the rest of the series/flims either on Platinum volumes or Renewal fansubs.