First: did you download an rpm built for Fecora Core 2, or did you just download an rpm with the right name (mplayer) without regard for the distro it was built for? If it's built for Mandriva or SuSE (both rpm based distros) it could cause problems.
Second: you should only need to click (or double click, depending on how you have your system set up), and rpm (the RedHat Package Manager) should take over and install it for you. Then look at the Gnome menu, (probably a Multimedia category) and it should be in the menu. Click on it to start it.
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