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The library is a good place for free books.

I would say if your goal is web development then HTML first because often you want to have a markup to make PHP as they function and HTML as markup.

PHP is not hard and trust me, if you know PHP, then you also know python and LUA.
They are pretty much the same language with VERY MINOR differences.

Couple of tips for anyone who wants to learn to code:
You set an example goal and try to achieve it.
For example:

Make a working guestbook.

It is not so hard to do it and if you get it working you will get familiar with all the functions you used to make it. You will know what they do.

As you make more and more goals for yourself you can set your goals higher.
And in the end if you really want to you can even make a forum.

What i am trying to say is. Practice makes perfect.
Trial and Error is something you will do a lot when scripting.

Yeah, something I'd suggest, instead of religiously following the little examples and exercises in books etc, actually make something. It's all well and good doing the things they suggest like 'write a script that does counts up to 100', 'select the name and address of five people from a database', but they probably won't help much when you come to make something for real, so instead, actually make a website or something and incorporate what you learn into that, that's better than having one small script for each bit you learn. When you learn something new, try and add it in, and if you have a website and have an idea for something, try and figure out how you'd do it, look up the functions etc, you'll learn much quicker.

For Web Apps: HTML+CSS+PHP+Others like Ruby, Perl, etc.

For Desk Apps: C/C++/Python