First - Dreamweaver is not a "nice program" - it is the premier web design program and choice of professional designers. Anything else is a wannabe. Like Sitegrinder.
It is extremely important when starting out to learn how to setup your site files and folders. Each hosting company/server has its own particular layout for sites (my own company included) but essentially you want your Index file in the main root folder, an Images folder, cgi-bin folder, PDF documents, and folders for specific file types (Flash, MP3, etc.) . Doing this allows for better organization of the site. It is easy to recreate a site layout in the Site Manager - it has a site clone function.
All versions of Dreamweaver have tutorials for beginners that show you how to use the basic functions of the program and how to build a simple site. Since the Adobe - Macromedia merger, they've started putting the Tutorials on the Support and Developer's site, and that's where you need to start if you're using one of the CS versions.
Forget using Flash buttons for now - Flash takes time to learn, and for simple rollover effects you can achieve that with Java anyway using the Rollover Image placement in DW. Essentially you create two images, the primary image and the rollover image - the rollover image is what the image changes to when a cursor "rolls over" the image link. All you need to do is to create the images in Fireworks, Illustrator, whatever, then use the Rollover Image function in DW.
Rollovers can also be text images.
Linking - There are 2 ways to link to files/pages in DW, Relative linking and Absolute linking. This is similar to Relative file paths and Absolute file paths on a drive or server.
Relative links are links relative to 2 or more given files. For example, if you wanted to link to a file called Test from your index file (what you always name your main site portal file) the relative link would be /Test. However, an absolute link/path would be "http://www.yoursitename.com/test.html"
Anchor Links: Anchor links are links to content on a page from another part of the same page. You've experienced this whenever you click on a link and it takes you down to the middle of a page. The Anchor link tag is the Anchor icon.
If you have your Site files showing on the left or right of your workspace, then you can select the image you want to add a link to, then click on the Point to File icon in the Properties Inspector, then drag it to the file you wish to link to in the Files Inspector. This performs a relative link to the file from the source you linked the file to.
For absolute linking, select the item/image you wish to have the link connected to, the write the absolute address (URL) in the Link field of the Properties Inspector.
You can link to anything you wish to upload to your site server, or anything on the web that suits you. Relative linking is for links within your site; absolute are URL's outside your site. Relative links can also be absolute links.
Link borders around an image - when you create a Hyperlink to an image file, DW and other programs automatically create a link border around the image file, which frankly is a real pain. The way to avoid this is to enter 0 for the link border values. The same applies if you do not wish to have table borders/lines showing on your site page.
DW also has pretty good site templates, and more than what is shown in the startup window. Consider using one until your more experienced.
Learning and Tutorial Assistance
Adobe continued Macromedia's tradition of having a large developer's and designer community on their site. This is the place for you and other beginners to really learn about site building. DW itself has fantastic documentation and online resources that show you pretty much anything. If you want a good online course in DW and the other Adobe programs, I recommend Lynda.com. Their courses are easy to follow, and they have different subscription levels. You can even just by a training DVD, but it's cheaper to subscribe. The instructors are all Adobe and former Macromedia instructors that know the programs inside and out. They also just recently began issuing certifications for courses completed.
NAPP is another great learning resource. Though it's primarily focused on Photoshop, it's training resources and discounts on software and hardware are worth membership itself. I got my 2 year subscription back when I upgraded my CS3 Master Collection to the CS4 Master, and got Lightroom 2 as well.
You can access the Adobe online resource sites by clicking on Help in DW, then DW Support or DW Exchange. Click just on Help/DW Help opens the DW Documentation files, which has been vastly improved over the years. I've been using DW since before it was called Dreamweaver, and it's come a long way in the past 11 years.
If you don't know what Extensions are, look them up on the DW Support/Developers site. They're like macros that insert code for