Well as a webmaster you will still be writing HTML even with PHP :) PHP will allow you to manage your websites way easier as you can write pieces of HTML and then "include" them into your html for instance.
the php.net website is a great resource once you get started, especially the contributions in the docs. Before you get started you might look at:
http://webmonkey.wired.com/webmonkey/programming/php/
They have a few tutorials with a range of complexity.
Many use php as the way to talk to a database, thats where the fun starts! The LAMP -> Linux Apache MySQL PHP is the foundation of many a killer web site and web application.
Good luck!
barnamos
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