My first web design software was Notepad.
I took a FrontPage class, but for the first six weeks, we were forced to design sites strictly in HTML. While frustrating, I am glad I know how to directly tweak the code to get the results I want.
Then I studied Dreamweaver. The learning curve was greater than I had exected, but I learned to appreciate the software, and never looked back. IMHO, it is the best web design tool out there.
I discovered XSitePro when I started building niche and affiliate websites. Dreamweaver sites take a lot of time for me to build.
With XSitePro, I can build a great looking SEO optimized site within a couple of hours. While Dreamweaver is still my favorite program, I am using it less and less as XSitePro is such an efficient tool.