It weirds me out to hear that some people have problems with OS X when switching. I'm not insulting your intelligence, it's just that for about 5-6 months before hand I got interested in them and I started researching. I must have read every wikipedia article about Apple, Macs, OS X etc.
I must have also seen every youtube video out there about Macs, product releases, old Macworlds, WWDC's etc. So when I got my iMac, I knew the features in and out, but seeing them for the first time astounded me. I knew how to use expose, dashboard, photobooth, and the only thing I had problems with was the -+X being X-+ and being on the left.
Remember, two-finger right click, two finger drag horizontally, vertically and 360 degrees to scroll. The right click has to be configured via system preferences (blue apple>system preferences) I believe. Also, right click on the dock separator to turn magnification on if it isn't already, to turn on hiding, or to put it on the right or left.
Play around with the function keys to see what they do (F1,F2, etc.) I'm not sure the exact config on the portables as i've never owned one. Get to know front row (use the remote it comes with and hit menu) to browse all of your media files in a clean UI.
Cool little things:
-Hold shift when minimizing, maximizing, using expose, or dashboard.
-Click on one of your Dashboard widgets and hit command(also called comd or open apple, or just apple key)+r
-Hit cmd+option+control+8
-Drag around the tabs in safari, create multiple ones and drag them in and out of the browser. When the tab is out of the browser, let go and see what happens.
-Also in Safari, drag a link into the tab bar.
- Have fun with the Screen Savers
-Blue apple>System Prefs>Speech>Enable Speakable Items> Say "Tell me a Joke"
Just some cool things to get you started

enjoy.