In the docs you write:
"Limitations of CacheMyWork
* CacheMyWork is only able to cache your applications, not their documents
*It's not able to save and automatically re-open the open documents for most applications (except where those applications happen to store the document's filename and path on the process's command line, such as with Notepad). In fact, based on my research,
I'm beginning to believe that the only way to accomplish this is to install application-specific add-ins that scrape the inner "state" of the app's documents and caches that as well. I believe that's a hopeless pursuit.
* CacheMyWork is only able to cache the first instance of each application that it finds."
Have you considered using "handle" tool http://technet.microsoft.com/en-us/sysinternals/bb896655.aspx
or alike? it maps all open files to owner processes. This can address both of the issues in the "Limitations"