This is the wrong way to start. Find HTML and CSS tutorial sites and learn as much HTML and CSS as you can even before touching Dreamweaver. If you can do that, then Dreamweaver will be very easy for you to use. Can't really speak for Photoshop, but it's fairly easy only using it to create graphics for web pages.
HTML, CSS & Web Design Theory Tutorials -
Photoshop Tutorials for Beginners