I used to do printing and it was loads of quark/photoshop stuff. Holding down all different shortcut keys all the time, I'd often unwittingly minimise/maximise something while still holding down shift and it'd happen in slow motion.
It took me literally over two years to twig what it was that made it happen
Other odd little bits I've found out or been shown...
• If you go to about this Mac and click on where it says Version 10.6.4 or whatever, twice, it shows you the serial number. Handy.
• You can drag a folder that you're in by the tiny little folder icon at the top of the window. A customer misunderstood me and did it, and it worked, so I just didn't say anything
• I was impressed that you can exposé within Spaces, I tried that straight away but didn't expect it to work for some reason
• If you hover over a date or phone number or address in an email in Mail, it gives you the option to add it to iCal, add it to Address Book, or look it up in Google Maps
There's loads more but those spring to mind straight away