Upgrade both.

Stuff's getting pretty cheap; you could get a T-bird mobo and a GF3 Ti200 fairly cheap on the FS/T forum - could probably get all of that for the price of a new GF4 Ti.
Biggest thing that the processor would bottleneck would be games like Giants, with lots of polygons, large maps, and the AI of multiple enemies at once. Plus if you are on a slower proc system like a K6-2, the bus transfer speeds will be a lot lower than newer systems, which will also help to chain down a powerful video card.
I guess having a GF256 and a fast processor probably would be best; the video card could then operate at its full potential. Plus it would be easier then to just upgrade the video card in the future.