How often do you need to do this?
If you use File.WriteMap to create a settings file, you can open that directly in Excel; in the version I have (Mac, 2008), choose File, then Import. Select CSV, and then on the second page of the wizard, set the delimiter to =. You'll end up with two columns, one with the keys, and the other with the values.
To go the other way is a bit fiddlier, because what you'll export is a CSV rather than a settings file; you could probably mangle it back into a settings file using a Word Macro to search and replace (strip " off the start of each line, and change "," to an =, strip " off the end of any line, or something like that). Then you should be able to read it back in using File.ReadMap.
Alternatively, if I were doing this a lot, I'd stick with the same option for exporting, because I wouldn't have to write any code. For importing back to the app, I'd write a bit of code read the CSV file from Excel, do whatever substitutions are necessary, and re-populate the KVS.