You will definitely want to start with the TV show. Even though the original DVDs are still out there (and probably at a pretty low price), picking up the Platinum edition thinpack is the best buy for you, as you'll get all that you need (except for
End of Evangelion, which you need to buy separate) to enjoy the series.
The best reason to get Platinum is so you can have all you need to follow the two separate paths the story takes -- the original cut and the Director's Cut (aka the "prime" episodes). The original cut is the on-air 26 episode run, which are all in Platinum. The Director's Cut diverges at Episode 21 and is number 21' (21 "prime"). From there, it goes 22', 23', and 24' -- these four are in Platinum's 6th and 7th discs. After 24' is
End of Evangelion, which is actually episode 25' and 26'.
Only after watching the TV show should you give Eva 1.0 (or 1.01) a view. I'd caution you not to see it first because 1.01 goes right through the first episodes of the TV show in a rapid way reminiscent of
Evangelion: Death. It's certainly one to pick up if you liked the TV show and wanted to see a few alternate takes on it (and the 5th angel fight, which is completely redone into a masterpiece battle sequence imho

)
(Also, while
Death & Rebirth may be nothing more than a recap-meets-End of Eva peek-ahead, the extras that come with it are nice enough -- including an encyclopedia of the Eva universe. Still, if you can get
End of Eva separately, that's the only one you really need.)