There are two areas of focus on compatibility in your message. One is file format compatibility and the other is feature set/interface parity.
While you are using LibreOffice 4 and Microsoft Office 2010 for Windows, and this is a Mac forum, we can still include Mac Word in this thread because the issues are the same.
There is probably a combination of file formats and settings that will work well for you when round-tripping documents between LibreOffice and Microsoft Office.
LibreOffice is based on the old (.odt) file format and its feature set is roughly equivalent to Word 95-97. LibreOffice uses conversion routines to produce OOXML or the older (.doc) file formats. Because the LibreOffice developers have done a lot of work
on bringing LibreOffice up to date with OOXML (.docx) file format, I recommend this format when round-tripping files between LibreOffice and current Microsoft Word versions (2010, 2011, 2013 and the next new version for Mac when it comes out). There may be
times when sharing using the old (.doc) format works better for a given document, so if OOXML doesn't work for you, then(.doc) remains an alternative.
Current Microsoft Office is based on the current OOXML standard open file format (.docx) and has had many features added and modified since 1997. Because OOXML is the current standard, I recommend saving in this format as the first choice, and again you
have(.doc) format as an alternative.
Files saved by LibreOffice will open in "Compatibility Mode" regardless of file format in Microsoft Word because LibreOffice's feature set is not identical to Microsoft Word's. To keep the interface and feature set behavior as close as possible to each other,
Microsoft Word can be configured to act like previous versions.
On the Mac, go to Word > Preferences > Compatibility. Click the pop-up for Recommended Options for and choose Microsoft Word 6.0/97. I think this option would be the most similar to the LibreOffice behaviors.

On Word for Windows, go to File > Options > Advanced and you will find a similar setting:

In Microsoft Word you can turn compatibility options on and off individually until you arrive at your own ideal combination for working with LibreOffice. If there is a particular combination of settings you find work best, please post them in a reply so
that others can give them a try.