1. There are several differences from PHP4 to 5. So many in fact that they recommend everyone look over their PHP4 scripts after converting to 5 to make sure nothing is broken. PHP5 does create a lot of structural language changes to be more in line with an object oriented approach including adding full constructors / destructors, adding interfaces and allowing them to restrict class usage, the ability to add set and get property "magic" methods and the introduction of new extensions / classes. That is in addition to a slew of ordinary upgrades and modifications.
This is not to say that all PHP4 scripts will break when going to 5, but there is significant changes which can affect your scripts.
2. Templates are usually a good idea for any system, not just a game. However the problem with a template is that if you make a mistake you have to usually correct several templates or templates which have been inherited from those bad templates. Sometimes they are a bit overboard with smaller streamlined games which you seem to want to make. The custom HTML pages are typically a nice dirty and cheap way of doing things, but down the road they can get tedious to upgrade and you will find yourself having to repeat an update over and over again for each "custom" page.
3. I always use moderation when it comes to developing object oriented projects in PHP or any web scripting language. Sometimes they are great for nice concrete things, adding design patterns etc. But not everything needs to be an object or contained in an object. Sometimes that nice little time difference function just needs to sit in an include file for later reuse.
4. AJAX is heating up in the PHP gaming market but at a slower pace than what some people would like simply because the good games out there were built in a more legacy code way and not very flexible to accept AJAX. You can certainly use it for different things than just a chat system. You could use it for minimap features, drag and drop weapons or armor to and from units, and even create somewhat animated game play with it.
I hope you find the tips useful in the future. Enjoy!