Get a good text editor like Text Wrangler, or Text Pad. Also get a good HTML Reference Book like the HTML, XHTML, and CSS Bible. Then just practice.
For the most part, I use Text Pad for hand coding, Text Pad allows you to create and save code snippets that you can reuse on any pages, this helps saver a lot of time and typing.
If you constantly use Dreamweaver, it will be very hard to learn how to hand code. If that is your goal, get out of Dreamweaver and force yourself to work from scratch. maybe not for a clients website, but create a hobby site for yourself.
If you get caught on syntax for something, Use your reference book, or open up Dreamweaver and create it on a test page, study the code, don't copy it. Force yourself to study the DW code, then write in manually in Text Pad.
When hand coding, good indentation practices are a must. DW is not very good at indenting code properly, it makes for very difficult to read pages. Trying to troubleshoot a problem in badly indented code is tough. if you are going to learn to hand code, you'll also need to learn to troubleshoot. learning to troubleshoot starts at indentation.