I think a good place to start is - what do YOU like to do? If you like programming, then I'd definitely look into learning PHP / MySQL. If you like graphic design, then learn photoshop, dreamweaver etc.
The bottom line, make sure you're doing what you want to.
There are a lot of factors in web development and a lot of different needs as well. You can me a "renaissance man" style developer that knows some graphic design, some programming, but not be a real expert in any of them. The advantage of this is there are a lot of smaller projects out there that need this type of developer (think mom-and-pop shops / local work).
The other route would be to focus on one aspect (programming, database, design, etc). These are typically higher paying jobs, but also usually harder to find.
The choice is ultimately yours. My only advice is to do what you love because you love it, not for the money.