What programming language to start with?

It depends what you're looking for, the languages are all essentially for different things. If you're wanting to understand how a website looks and feels, look at HTML and CSS. If you want to learn how websites function client-side, take a look at JavaScript or jQuery. If you want to look at how they work internally and things such as login forms, cookies, custom feeds etc work then look at PHP and MySQL.
I'm not sure what Python's even used for, I've never used it before but the Visual Basic language is very simple to understand and is essentially psuedocode in it's own right.

At the minute I'm messing around with Pawn which is just an offspring of C.