Many laptops had both VGA and DVI connectors so that you could choose to use either, not both. If your rig is capable of running 2 external monitors, the OS should autodetect that for you and show up somewhere in "Display".
If your video card have something like 2 video interfaces for everything - yes you really can do it clearly. It really depends, but you should be able to use something like VGA and DVI with ease here for as many cards as your monitor have seriously.