You're going to have to check the manual to see if it will do dual monitors, but I don't think it will. Just because a card has two outputs doesn't mean you can do it. I had an Elsa GeForce2 Ultra back in the day, and I seem to remember (althought it's possible I'm dead wrong) that the only cards from the GeForce2 chipset lineup capable of doing dual monitors were the MXs. Even then, it was the card makers decision as to whether they wanted to implement it or not.
As for the primary monitor question, during post and bootup, I think it depends on the card. I had one that would display identical images on both monitors before it booted into Windows. The card I have now only shows bootup on the monitor connected to the VGA output. Once in Windows though, you can set the primary monitor in the display properties. This is the one that games and other video applications will play on.
Edit:
Here a couple links to nVidia's website. You'll notice that TwinView (nVidia's name for dual monitor capability) is listed as a feature on the GeForce2 MX page but not on the GeForce2 Ultra, Ti, Pro, GTS page.
GeForce2 MX
GeForce2 Ultra, Ti, Pro, GTS