This is probably the only time in your career when you have complete freedom to choose which tools to use, so use it in the best way. Explore some of the classic tools that go a long way with you.
So instead of using the IDE, which you are likely to do all your professional life, you will get a taste of using old school editors like vim / emacs. One of the advantages is that the IDE will not hide all the details about how your project will work, knowing that a full technology stack is always a plus.
For any technology that you will use, try and get a good broad perspective before you dive into the implementation details, so for PHP I would suggest getting an idea of XHTML, CSS and Javascript, including libraries like jQuery; Relational object mapping (look at Ruby on Rails, CakePHP, Django, and SQL Alchemy) and Model View Controller Frameworks across platforms.
For PGSQL, in addition to normalizing, try to penetrate the depth of information and calculate transaction isolation levels and when they will be useful.
It is also important to understand how the HTTP protocol works at a low level and how highly scalable websites can be created using HTTP.
Instead of relying on tools, I would say that simply create a reading list on the topics mentioned above and which will automatically structure your thinking process to take these problems into account.
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