When I had to make my first (reasonably) professional looking CV while applying for undergrad Co-Op jobs last Winter, I chose to do it Latex and tweaked the moderncv template (http://www.ctan.org/tex-archive/macros/latex/contrib/modernc...).

Since nearly everyone else's resume is written in Word or some other word processor, every employer noted that it was exceptionally well done.

Time well spent : ).