The "Robert C Martin" book, which was actually written by Michael Feathers ("Uncle Bob" is, it seems, a brand name these days!) is a must.
It's near-impossible - not to mention insanely time-consuming - to put unit tests into an application not developed with them. The code just won't be amenable.
But that's not a problem. Refactoring is about changing design without changing function (I hope I haven't corrupted the meaning too badly there) so you can work in a much broader fashion.
Start out with big chunks. Set up a repeatable execution, and capture what happens as the expected result for subsequent executions. Now you have your app, or part of it at least, under test. Not a very good or comprehensive test, sure, but it's a start and things can only get better from there.
Now you can start to refactor. You want to start extracting your data access code so that it can be replaced with ORM functionality without disturbing too much. Test often: with legacy apps you'll be surprised what breaks; cohesion and coupling are seldom what they might be.
I'd also consider looking at Martin Fowler's Refactoring, which is, obviously enough, the definitive work on the process.