When adding another card to a single card system, you should check the nVidia drivers tab and write down the bios version on your existing card. Power down the system, remove your existing card and install the new one. Boot up and verify that both cards have the exact same bios version. If they are the same, you're golden, if not, one of them will need to be flashed so that they are the same.
After you're sure you have the same bios, switch the SLI card to the dual position, install the new video card, install the SLI bridge between the 2 video cards, and plug in the mobo molex (with 6800's- plug in the 6 pin power plugs to the cards).
You didn't mention which motherboard bios you're running. With the early bios think you would need to enter the bios and change the SLI setting to dual cards.
Now you should be able to boot up and set up the drivers.