The answer is yes. Win2K natively supports dual monitors.
For the most part, you should be able to plug in the PCI card, turn it on and go.
If you only get one monitor, you may need to modify your machines bios. In the bios, make the PCI card the primary graphics card. In Windows, make the AGP card the primary graphics card. Then boot up and try it again. (Note that you may not need this last fix so don't try it unless you need it.)
Jeffrey