The manual will be best best place for what functions do behind the scenes. I used the book Core PHP5 and found it to be a good point to learn almost all of the functions in existence.
I've found the best way to learn is to try to do something somewhat complicated (your own blog, an simple estore, web site scraping, etc...). You'll start learning lots of functions, tips, techniques and methodologies from tutorials, the manual and this forum.
Also, once you have a good grasp on syntax, start Object Oriented programming. No sense in starting with procedural (line by line, with some functions) when you will eventually end up at OO.
I've found PHP5 Objects and Practice, Gang of Four Design Patterns and Martin Fowlers Patterns for Enterprise Application Architecture very interesting. I really wish I started with those sorts of things earlier on in my PHP career, which only consists of 6 years.
HTH