What would you suggest I do if I wanted to try and start learning PHP? About all I know is some HTML and some CSS in a very hack style guess and check manner (which of course sucks)
Any suggestions on the best way to get the basics down?
Honestly, I only know PHP because of WordPress. I say that because, IMHO, if I can learn it, anyone can.
I would start with the Codex, learning the WordPress template tags and functions. After that, if you need to learn PHP, I would recommend the PHP Manual and w3schools.
For specific questions, your best bet is to start with a simple Google search for "how to do X in PHP", and then go from there, using the PHP.net manual and w3schools for help with implementing specific functions.