I only have the one video card, with dual DVI out. So I don't think I can help. - Since getting two identical LCD flat panels, I have always gone for cards with dual DVI out, - I can get two identical high quality pictures that way. - Much better than using a D-sub VGA connection.
However, I don't think the VGA connection should be causing the problem you are having. I would have expected the nVidia settings to allow you to set up the two 22" monitors in any combination you required, - so I'm rather stumped!... Sorry!
Could I suggest you try a card with Dual DVI out + TV out, all on the one card? ..... Just a thought.
ps, .... After adding the extra card, and installing latest drivers etc, have you also tried reinstalling DirectX again?
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