With all this talk of advanced users, thought I'd share the power of the Win key, which was once shared with me and for which I am eternally grateful.
Win-R: Run dialog
Win-E: Explorer
Win-F: Search Computer
Win-Break: System Properties
Win-D: Kind of the same thing, but works better - show desktopWin-M: Minimize all (shift-win-m unminimizes)
Win-L: Login screen
Win-Tab (and Shift-Win-Tab): Cycle through open items in the taskbar (use space to open it)
There's tons more (Google it). The ones on the top are the ones I use most often, run and explorer especially.
Anyone who knows me will know that I use the mouse as little as possible. Lots of alt-tab, ctrl-shift-tab, win-this, win-that. That's part of the reason I hate it when websites don't set the accesibility tab index for form input. Don't make me tab through a bunch of links and navigation if you know all I want to do is login anyways.
(Speaking of which, this stupid rich text box won't let me tab out :)