The two nVidia references refer to the two controllers on the board: The Northbridge and the Southbridge.
Windows XP x64 will allow for full use of a 64-bit CPU and allows you to break the 3GB limit imposed by Windows XP x32. Since he wants to do Photoshop it's vital to have lots of available RAM.
Since it's 2D work involved he won't need the power of an X2900 or an 8800 series. A basic little X300 or 6200 would do it with ease. SLI is completly unnecessary in this case.
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