4, 5, 2, 3, 6....then 7 of course
thats actually genius, never would have thought of that. i was a purist of "release order" but that makes a ton of sense and makes it much more palatable.
IV and V are the primary story and should be seen first
that leaves you with the cliffhangers in Empire (Vader is Lukes dad, Han frozen)
skip I - it really adds nothing as it says. every single person either dies and is no longer relevant or has much bigger parts in II and III that shows their full character arc (without being played by a kid, and it keeps you from thinking Padme is a cradle robber too) and the bonus of very very little jar jar binks or the gungans. Maul, Qui Gon are dead, Watto is irrelevant and also no virgin birth and midichlorians nonsense. Other characters are better represented in II and III (Mace Windu for example).
II and III give you a nice flashback basically then in the interim and fully explains Anakin/Vader and Obi Wan
end with VI then jumping back to the destruction of the Empire and Luke's ultimate victory - and as a bonus the ending with Haden Christensen added into the Jedi ghost scene makes sense (whereas it does not in release order).
I love it - BES - tell me what exactly anyone would miss from episode I??? some of the politics and clone army origin i suppose. but its unneeded.