I'm using the 258.96 drivers, and I have my centre monitor hooked up on the primary DVI port of the first card. In nV Control Panel it's listed as monitor 1, with the leftmost being 2 and rightmost being 3. If I launch a game at 1920x1200 with Surround enabled (as it takes too long to switch, I leave it on permanently) it's automatically on the centre monitor...?
Exactly. Primary card > center monitor and you're good to go.
That's the difference between TripleHea2Go and 3-way SLI:
-On TripleHead2Go, your monitors would be connected as they are on your desk (Left output = Left panel, Middle output = Center panel, Right output = Right panel).
-With Nv Surround, they are connected in order of "importance" (Top card = Center panel, Second card = Left panel, Third card = Right panel).