Using Form.TopMost will make the window appear above any other window in your application, but it does not work other applications.
While I have seen apps that make their window float on top of all other windows, I don't think you can make a modal dialog box that prevents you from using other applications.
A really dirty hack would be to have a timer the forces your window to the foreground every second. It means that users would not be able to use any other application in a meaningful way, but they will definitely hate you for it.
You could also try simulating the Windows Vista/7 -style UAC dialog by taking a snapshot of the desktop, making a full-screen window with that image in it, and then rendering your window on top. However, experience shows that users don't like those UAC dialogs either.