Many settings in php.ini can be overridden in the .htaccess file or in the executable script itself. Take a look at the list: http://us3.php.net/manual/en/ini.list.php and refer to the Changeable column for more details.
If by extension you mean the php extension, then no, you cannot have another php extension on the same server, because php is shared. The only way you could do this is to start the 2nd Apache server. If this is really a test site, a separate server will be possible, because you can run it on a separate port, but I would not suggest taking this route if you were not confident in your skills as a Windows system administrator.
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