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Generally, I like to Evolve in this sequence: Q-E-R
but you may do this: E-Q-R
Or this W-E-R
or this W-E-Q
note that the first one is generally the best choice as of now.
Following the not-so-recent nerfs (as of 08/25/13) to Kha'Xix's W, Void Spike(s), many players have opted to evolve Q over W first. Also, some of they chose not to evolve W at all.
Q increases your attack range and Q range and significantly increases the damage on it (like a lot).
W makes Kha'Xiz shoot three spikes, in a cone, spread equally apart. Basically more poke and wave clear.
E makes Kha'Xiz jump farther, and the jump resets after you get an assist or kill, which is good for multi kills or tower diving. You can leap over every wall in the game when evolved.
R gives Kha'Xiz 3 instead of 2 uses for his ult, and while in stealth, he takes 50% reduced damage. Great for chasing/running away/reducing damage (obvs).
Q is really nice now, since you don't need to isolate to deal a ton of damage. I usually (90% of the time) evolve this first.
W is only really needed if your team lacks wave clear or poke, so you don't evolve it if so. Evolve it last.
E is for getting pentakills. Just kidding. By evolving this you can turret dive and escape easily. Evolve this second or first.
R is great for reducing damage and confounding your enemies. Evolve this last if they have a lot of AoE (area of effect) damage (i.e. Anivia, Zyra, etc idk).