Sorry, I missed the bit about PHP 5. As was suggested before learn PHP 4, and then the extras that come with PHP 5.
PHP 5 is a lot better, but isn't that widely supported yet, but if you can use it its a good idea too. I`ve always used my own server or VPS so its never been a problem, as I installed it myself, but a lot of hosting accounts don't allow it yet, although that will slowly change.
Compatability wise, its easy to go from PHP 4 to PHP 5, and existing scripts will need little modification, and the modifications are very simple things. PHP 5 is a bit stricter in terms of programming style, its a shame PHP 4 wasn't like it as it encourages good programming skills, and thats where the modifications come in, things you could get away with in PHP 4 you can't in 5.
PHP 5 has quite a few new commands which make life easier, if you use them you can't go back to a PHP 4 server.
So concentrate on learning PHP 4, and 5 will be easy to adapt to.
The best resource out there is the php manual, and even experienced programmers use it a lot, as there's no way you could remember all the commands
A good PHP programming environment helps a lot when your learning, such as Dreamweaver 8 which has syntax colouring and code hints, and makes it lot easier to write scripts, as as soon as you type a PHP function name for example, the parameters you need to give the function are shown. Also shows you if you have used a function name that doesn't exist, or is spelt wrong.