to choose what monitor has the start screen and metro, you can either click in the lower left corner of the desired monitor or you can drag the metro app to the monitor that you want with the mouse or your finger. your second monitor will automatically be the desktop monitor.
I don't think you can have metro apps on multiple monitors at the same time. not sure though.
for spider solitaire, are you referring to the Windows 8 version? or the Windows 7 version?