The option to print both sides like a book is available in Word 2007. It will only show as an option if your printer supports double sided printing, same with all the versions of windows to best of my knowledge. Automatic double sided printing is known as Duplex printing, the other alternative is manual turning of pages.
So first off you need to deteming the capability of your printer.
When you select Print in Word you need to open printer properties, if double sided printing is available for your printer it should show there somewhere, I can't tell you exactly as each printer has it's own dedicated printer software.
To make Hoster automatically open Word from within the songbook dialog you need to use the "Select Viewer" tab then brows to the folder containing the "WinWord.exe" file, select that.
Where that file is on your computer varies somewhat.
Watch this video of mine on finding winword.exe:
https://www.youtube.com/watch?v=wYOjPxBa-Eo
It's an old video and I was using windows 7 with Word 2003 but the principle is the same for all versions of Word.
I now have windows 10 with Office 365 but finding the file is much the same, just remember to right click and select "Open file location" not to just select it.