Switching to MAC and need help
The PDF version of the user guide linked above is for Leopard (Mac OS X 10.5), which is 3 versions behind the current release of Mountain Lion (OS X 10.8). An HTML version of the current VoiceOver Getting Started Guide is available from Apple's VoiceOver Downloads page, along with other resources, such as keyboard charts of the VoiceOver commands. Alternate formats, such as RTF versions of the Voice Over Getting Started Guide for current and past versions of Mac OS X, can be found at John Panarese's Macfortheblind documentation pages under the heading for "Manuals and User Guides". Users with new Macs can always access the VoiceOver Getting Started guide in their selected language from the VoiceOver help menu.
There are many ways to minimize the number of keys pressed for VoiceOver commands, or modifying their locations. Cliff has mentioned a few options, including locking down your VO keys with Control+Option+semi-colon, which is particularly useful when working in tables, and enabling single letter navigation of web pages when QuickNav is turned on, You can also customize shortcuts with Keyboard Commander, or customize gestures for the TrackPad. However, you can extend options by using a third party application like KeyRemap4MacBook. Take a look at Eric Caron's post in the AppleVis guides section on Remapping the Keys on your Mac's Keyboard to Enhance the VoiceOver Experience and then go to the page for his podcast. Eric has his Caps lock key configured to be used in place of VoiceOver's Control+Option, and to also work as the JAWS key in his Windows VMware setup. Another VoiceOver user I know has additionally remapped the "Return" key on the right side of the keyboard so that, when pressed by itself, it functions as a normal return key, but when pressed in combination with the right command key, it operates like the control key -- effectively giving her a pair of VO keys on the right side of the keyboard. There are many other customization options you can do. Please read the comments on the podcast page, because there are a few changes in the latest version of KeyRemap4MacBook. You will also find a link to Mac-access list post that gives additional information about using using KeyRemap4MacBook.
HTH. I won't repeat all the other useful resources for switching to the Mac that have already been suggested.