I disagree, your best to design your site in photoShop and then use dreamweaver to put it all together. You need to learn some html basics or you wont understand how to lay your pages out.
Not all three I would advise that you try to find a tutorial on HTML for beginners. Just to understand the basics and then try to learn DreamWeaver if you have it if not frontpage does the same job. Dreamweaver has a lot of good tutorials that come with it so thats why I would reconmend it.
I would buy a great book. HTML for the World Wide Web-5th Edition by Elizabeth Castro. Its a great book for beginners. I'm in my second web design class in school, and it used as out textbook. Program- Try Photoshop, Fireworks, and Dreamweaver. Those are your best bets.
Hope this helps. My 2 cents :D :p
Use Dreamweaver MX 2004. I used GoLive and Frontpage and neither of them are as good as Dreamweaver MX 2004. I also used to hand code in notepad, but that takes forever.