if on kde4, in the taskbar(can't remember, my desktop is really modified) press the two tools button called configure your desktop
in that window open/hardware/display and monitor/size and orientation
there should be listed the vga and dvi and any other output detected
enable them as required, the other menu that says multiple monitors offers more options
of course this depends on the driver, i think that nvidia offers other options
And such is the problem- although my pc clearly recognizes both monitors and uses them as it boots up, as soon as it gets to the gui it does not use both. and in the hardware/display and monitors/size and orientation It does not list both outputs it only shows one-