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There's nothing to set up in Word really. Just use it correctly. The main mistake newbies make is to ignore paragraph styles. If your title is given Title style, your chapter headers Heading 1 style etc. conversion to EPUB will be very easy!
You can even use advanced Word features like making a Table of Contents, Index, Footnotes... Save a DOCX, drop it into Calibre for conversion, you may have a very nice surprise! (Other conversion methods are available, and have their disciples. I don't know how well they deal with the advanced stuff.)
The thing is, in Word don't try to be clever. Use the Word functions 'by the book', all will be good.
The Guido book seems to be obsessed with cheating the system. You really don't need to. Just use it!
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