One of the main reason developers use dreamweaver is its ease to create dynamic sites (whether it being php, asp, etc.) So you are headed in the right direction. Dreamweaver does much more than just static sites. Once you get a hang of it, you'll love it!
I am assuming that you want to test the site on your computer (testing server) first before uploading it to your live host - correct?
I use a mac, simply because it is so much simpler to use it as test server than a pc, but the process should be similar. Since you have MySQL, PHP, Apache (WAMP) working correctly this should be pretty painless.
Step 1 - In dreamweaver go to Site/new Site (use basic site definition)
Step 2 - Site Definition/Editing Files
Only fill in the "What would you like to name your site?" question. Leave the "What is the HTTP address (URL) of your site?" question blank.
Click "next>"
Step 3 - Site Definition/Editing Files, Part 2
Under "Do you want to work with a server technology..."
Click "Yes, I want..." then
Choose the PHP/MySql option
Click "next>"
Step 4 - Site Definition/Editing Files, Part 3
Under "How do you want to work with your files during development" choose "edit and test locally"
then under "Where on your computer do want to store your files" input the path the folder where your site files will be and
Click "next>"
Step 5 - Site Definition/Testing Files
Under "How do you connect to your remote server"
choose "Local/network"
then under "What folder on your server do you want to store our files in" input the path the folder where your site files will be and
Click "next>"
Step 6 - Site Definition/Testing Files, Part 2
Under "what url would you use to browse to the root of your site"
choose Input the root folder of your site
Click "next>"
Step 7 - Site Definition/Sharing Files
Under "Do yo want to enable checking in..."
choose "No, do not enable..."
Click "next>"
Step 8 - Site Definition/Summary
Click "done"
you should be all set up. If not, the problem will mostly likely be that the root folder url (step 6) is not set up correctly.
Also here is a link to a great article on running php applications using dreamweaver:
http://www.sitepoint.com/article/macrom ... mweaver-mx
You can also go to adobe.com and check their support section as well. and the help section inside of dreamweaver can walk you through also.
Have Fun!