There are a lot of helpful articles and tutorials in the Getting Started section of the Dreamweaver Developer Center. To work successfully with Dreamweaver, you need a solid understanding of HTML and CSS. There are free tutorials for both at www.w3schools.com. Also check out Get up to speed with CSS layouts.
If Dreamweaver is acting erratically, or if you see a message saying "the following JavaScript error(s) occurred", it's usually a sign of a corrupt cache file. The first thing to try should always be to delete the file cache. If that doesn't work, delete your personal Configuration folder. Full instructions are in Deleting a corrupted cache file.
Note: Some tutorials are on non-Adobe sites
The Dreamweaver Cookbook contains a collection of articles describing how to perform a range of tasks - some simple, others more advanced - in Dreamweaver. You can also post a request for someone to provide a recipe for a particular task.
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