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I haven't watched NGE in a while, and to be honest I don't really remember it that well, so I can't really compare this to the series. What I can tell you though is that Evangelion: 1.0: You Are (Not) Alone covers the first six episodes of NGE, has the same awesome soundtrack, and it seems like they made Shinji less of a pussy, which is a great thing!
Eva 1.0 perfectly blends the 90's style animation of NGE with modern quality animations, making this one of the best looking anime ever in my opinion. Every scene just looks beautiful, and the action sequences are so bad ass. The story is well written but doesn't go that deep since this is only the first out four movies in the "Rebuild of Evangelion" series.
Overall I recommend this to both newcomers and fans of the series. Everyone Should (Not) Miss Out on this great film!