This blog post seems to offer a solution. In essence you run the following code to get the color from wherever the mouse is on the screen:
IntPtr hdc = GetDC(IntPtr.Zero);
uint pixel = GetPixel(hdc, currentPoint.X, currentPoint.Y);
ReleaseDC(IntPtr.Zero, hdc);
Color color = Color.FromArgb((int)(pixel & 0x000000FF),
(int)(pixel & 0x0000FF00) >> 8,
(int)(pixel & 0x00FF0000) >> 16);
I'm not sure how much I should copy up here, but if you download the source code from that page, it should answer a bunch of your questions.
And, if that does not work, take a look at this answer: https://stackoverflow.com/a/1483963/1043380