Internet Explorer: When should I use Compatibility mode vs. Enterprise Mode for IE 11?

Both modes are actually additive and not exclusive. For details, please see these Microsoft articles.
PolicyPak’s job is to populate those lists for you dynamically instead of having to make your own lists.

http://blogs.msdn.com/b/cjacks/archive/2014/08/11/ie11-enterprise-mode-and-compatibility-view-are-additive-not-exclusive.aspx
http://blogs.msdn.com/b/ie/archive/2015/04/23/announcing-improvements-to-enterprise-mode-and-enterprise-site-discovery.aspx

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