There is currently no way (that I know of) to send the Win+X combination to access the power user menu in a Windows 8/8.1 host and the support for control sequences with the keyboard is really limited having a preset of "combos" to choose from.
It would be interesting to have a mode you could enter (and implicitly when you go full screen controlling the other machine) so that any key combination you press is directed to the remote machine.