I'd like to give users of a desktop app I'm working on the option of accessing their local code either through the Windows Explorer/Mac Finder or through the command-line, what's the best way to do this? I also want to display the local file path to their code directory.
SourceTree has a great example of the workflow you're mentioning. I'm not sure of the use case for your specific example, but in SourceTree, 95% of the time you're just looking to open the repository.
As a result, SourceTree has created a default action of clicking on the item in the list to open the list, and has buried other actions under the right-click context menu.
If you want to provide access to some other actions without using Right-Click, a "more options" button at the end could also work well. Box.com has an excellent example of the default action being to open, the first promoted action is to share and then all the other options are in the overflow.
In your example, I would recommend determining which one of the actions is the primary action, and then burying the other action in a Right-Click context menu (as you have said, this is a desktop app and right click is available).