Yes, MS Word/Publisher/et al have HTML output, but don't use them for this purpose. They produce very poor results - even an experienced designer would struggle - and very dirty code.
I'm currently teaching myself CSS and it really isn't too bad. Honest. But you should stick with the WYSIWYG approach - as I did until recently - because it's easier for anyone who wants a simple website. Find a free copy/download of NOF 8 or Serif Webplus. I would recommend NOF; it's capable enough to design commercial sites if you know what you're doing, so a first website is no sweat for it.