Okay, well your main is connected through DVI and secondary through VGA, as long as both of these ports are on your video card then you should be able to activate them by right clicking on your desktop background and selecting screen resolution, you should see 2 monitors in the graphic, if not then your computer does not see the second monitor, if it does but number 2 is grayed out click on it and select extend desktop check-box.
If this doesn't work there may be some driver issues which means you just reinstall the driver from the disk that came with your card or from online support.
Only one is plugged into my video card..- The other one is plugged directly into my computer. Is that a problem?
This is what I see AFTER I've already done the Windows Button+P option and selected "Extend".
Do you think it could be a monitor problem? The monitor I pulled out as my secondary is quite a few years old.. XP era. I wouldn't think that would be a problem, but who knows. When I try to do anything on the secondary monitor (access the menu manually via the buttons in the front) it says 'In Power Save Mode' 'Press any key or move mouse.' I do both, but nothing.
EDIT: If I go to the 'Screen Resolution' page BEFORE I press Win+P and selected 'Extend', then it only shows one monitor, my primary.