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So, I'm going to start painting my Necrons tomorrow. I'm going with a fiery/molten theme.
Examples:
http://i87.servimg.com/u/f87/13/57/54/46/untitl10.jpg
http://th01.deviantart.net/fs49/200H...m_by_Vij_8.jpg

Now, what my question is, which priming base should I use to get my desired result? Black or white?

I say black. It gives you better shadowing, in my opinion.

I prefer Rustoleum Auto Primer, myself, but individual tastes vary.

Could prime white, then basecoat red (or just prime red)and wash black a few times. That will result in the raised surfaces being red and the recesses black which may not be what you want. It could be a good, easy base to work from after which you could do some free hand sparks/bright spots etc. It's just that putting red on black can be annoying. But if it won't result in the look you're after you might need to prime black and spend some extra time getting the red to look nice.

Yeah. What I'm planning on doing is yellow, then orange, then red like how people paint lava. Then try to use red or orange to paint a glowing effect around the edges of the recesses and eyes