So - management is looking to do a push to move towards doing unit-testing in all the applications moving forward - and eventually get into full TDD/Continuous Integration/Autom
I think it will be harder to start with test-after type of testing. A major difference compared to test-first is that test-after does not guide you in writing code which is easy to test. Unless you have first done TDD, it will be very hard to write code for which it's easy to write tests.
I recommend starting with TDD/BDD and after getting the hang of that, continue learning how to do test-after on legacy code (also PDF). IMO, doing test-after well is much harder than test-first.
In order to learn TDD, I recommend finishing this tutorial. That should get you started on what kind of tests to write.