I don’t belive in trying to learn too many shortcuts at once. Here are 5 which have made my life easier on Windows 8 desktop:
Alt F4 shuts down open windows but on the desktop it brings up the shutdown/switch user box
Windows key X brings up a list of useful options like Run, Disk Management, Device Manager, Search etc
Windows key C brings up the Charms sidebar
Windows key R brings up the Run menu
Windows key F brings up the search menu for files in the Metro interface and I really like that GUI