Can you remap keys to only be used while using VMware?
The answer to the question is yes, you can.

VMware Fusion (from v2) provides this built-in to the application (and incidentally Parallels provides almost identical functionality)

Under VMware Preferences -> Keyboard &amp; Mouse you can turn on/off the mapping of keys to other functions.

This document over on VMware's document repository itemises how.

This video over on Vimeo shows how it works in practice (the video shows it working in Fusion 2, but the functionality hasn't changed drastically since).