Hi Ray
I'm afraid that you're heading into a bit of a dead end here.
For a static site yes. But Zen Cart is what's known as a dynamic site, i.e. it uses information from a database to decide which pages to display and what data to show on them. Dreamweaver does have some facilities to do this, but they're not very good and not compatible with how Zen Cart works.
Zen Cart has a default template that does most, if not all, of what you would want. You build your own template by placing additional files into a parallel folder structure to "over-ride" the way the default template works to make it function differently or change its look. Templates that can be purchased (or downloaded for free from this site) simply speed up the process of building up that parallel folder. Beware though some of the commercial templates. They can sometimes be out-of-date or inhibit Zen Cart functions if not implemented properly (and there are a few out there that aren't). Yes you an use Dreamweaver to edit your templates, though in Code mode rather than WYSIWYG.
Dreamweaver is a visual editor, but what you describe is a code generator. You can layout things that won't change visually and it will translate this into HTML. You can use it to insert blocks of dynamic PHP or Flash, but you would have to write them yourself, and Zen Cart is the other way round. It's a dynamic application with blocks of XHTML inserted.
My recommendation would be to start by building your own simple template. You'll end up going through the same steps with a paid for template anyway, but understand better what you're doing. Yes, you can use Dreamweaver, but it'll never come out of code view and my copies destined for the bin shortly.
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