In my decades of experience using Word on Macs, and WIndows in the corporate world, one rarely needs to deviate from a few ribbon bar selections for most documents. This is not defending the horrid interface, but in my experience, I set aside the emotional baggage/expletives, and focused primarily on the particular deliverable. There are also nice thick Word books as backup.
All of the MS Office clones have duplicated the ribbon bar to some extent, and using LIbreOffice as an example, have the highest compatibility with the Word .docx format. LibreOffice supports Master documents which would allow you to break that monolithic document into convenient chunks (e.g. chapters). You might look at Mellel, or NisusWriter Pro to see if they can help you escape from the MS interface. Both have demo software on their websites.
There is a LibreOffice Writer manual (written in Writer) that may expand on whether it can export document bookmarks to PDF, or that you need something more heavy duty like InDesign.