Well first of you should ensure that the php.ini file you're looking at is actually being parsed at all by PHP. Make a change in a PHP core directive, e.g. turning display_errors Off (or On). Restart Apache and see if your change is reflected in a phpinfo() printout. If not, then we need to get PHP parsing your php.ini file first.
Second, verify that you have a libmysql.dll file in the root of your PHP directory (e.g. c:\php).
Finally, verify that the root of your PHP directory has been added to your system's PATH environment variable.
EDIT: Also note that the [man]MySQL[/man] library of functions has been deprecated in favor of the newer, much improved [man]MySQLi[/man] library (or even [man]PDO[/man]).