I don't think his 512MB card is holding him back right now. Sure he may gather a few more frames in games like Crysis, which loves VRAM, but adding a second card should still substantially increase his performance such that it two 4870s with an effective 512MB of VRAM should outperform a single 1GB HD4870 in the majority of games.
So yeh, I think adding a second card for Crossfire would be the best deal. And he could buy either the 512MB or 1GB version for Crossfire use, although the 1GB would be a waste if he doesn't plan to upgrade his current 512MB card.
Our fellow board member apoppin ran some benchmarks and published them. When comparing the 512MB and the 1GB HD4870, in every single one of his game benchmarks they performed identically even at 1920x1200. The games he tested were Crysis, UT3, Stalker, Lost Planet, HL2: LC, Fear, Quake Wars, and Call of Jurez. Really the only test he did where the 512MB showed a major disadvantage was in the PT Boats demo. You can PM him, or google search, for his results.