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If you value your life, don't start with Microsoft Word.
If it needs to be simple, you can look at anywhere that has pre-made themes/templates/whatever. Be advised, though, that they are pretty common, and won't be unique.
Hmm. There weren't any replies when I started writing this, but Publisher I think is geared toward desktop publishing, eg. print, and it may or may not be able to do web stuff. The Microsoft offering in the web department is Frontpage, which is actually very similar to Dreamweaver. It's actually fairly easy to use (graphical editor) and is WYSIWYG (what you see is what you get), so it's like using a word processor.
In any case, there's always Google Pages (http://www.googlepages.com). Last time I checked, it had a pretty intuitive interface (web-based) for creating webpages.
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