ProfileMatic does not currently have direct support for launching applications as an action. But you can use custom action to do it. Here's an example how to do it:

First find the file that describes the application to launch. As an example, let's suppose we want to launch the "Maps" application.

In terminal, find the file that describes the application "Maps":

From here I see /usr/share/applications/maps.desktop is the correct file.

In ProfileMatic:
Put into Custom Action the following code to start the application: