I learned the basics of MS Access because I needed to develop an asset management tool for use in my job. An $85 online Access course did the trick and I then taught myself some VBA by Googling what I needed and then picking through the code to understand what it did. I have now written several Access applications that are in productive use. I also have some self taught HTML skills after writing several websites the hard way in Notepad, although I now use Dreamweaver.
One day, when I get time, I plan to learn PHP and MySQL.