PHP 5.3 is a significant evolution of PHP with deprecated features:
http://docs.php.net/manual/en/migration ... ecated.php
This means that updating from 5.1.6 to 5.3 put your php codes at risk of breaking.
Centos is known to be a later adapter of new versions of softwares (like PHP 5.3) because it wants to be safe and reliable.
If you want a more cutting edge distro, go with Red Hat, not Centos.
You might want to get a new linode, install PHP 5.3 there and run your php codes to test them before installing php 5.3 on your main machine.