Start with Preferences
If you are a long-time Dreamweaver user, you will benefit from a careful reexamination of your work habits in order to take advantage of what Dreamweaver has in the way of help. The first step is to set the Preferences for maximum accessibility help.
In the General Preferences category, select "Use <strong> and <em> in place of <b> and <i>." Select "Use CSS instead of HTML tags."
Tagging elements with semantically meaningful tags such as strong or em is important for accessibility. The idea of using semantically logical elements to create content is a foundation concept that applies to other element choices as well.
Accessibility requires that you separate content from presentation. In order to do that, you must use HTML to structure the document with logical semantic elements that are clearly organized into headings, paragraphs, lists, and other logical content blocks. By using the generic HTML container div, you can add context to the structure to give yourself powerful descendant selectors for your CSS.
Demo: Semantic HTML
More information is available in The Early Bird Catches the CSS: Planning Structural HTML.
In the Accessbility Preferences category, select every option.

With these preferences selected, Dreamweaver will help you by reminding you to include labels on form objects, alt text with images, and other important accessibility attributes.
The number one accessibility need is effective alt text.
The References
Dreamweaver has a number of built in reference materials, including the UsableNet Accessibility Reference.

Page Checks
Dreamweaver will run accessibility checks for the page.