This depends very heavily on exactly how you intend to use threads. What does your program do? Where do you want to use threads? What will those threads be doing?
You will need to figure out what resources these threads will be sharing, and apply appropriate locking. Since you're starting with a single-threaded application, it's a good idea to minimize the shared resources to make porting easier. For example, if you have a single GUI thread right now, and need to do some complex computations in multiple threads, spawn those threads, but don't have them directly touch any data for the GUI - instead, send a asynchronous message to the GUI thread (how you do this depends on the OS and GUI library) and have it handle any changes to GUI-thread data in a serialized fashion on the GUI thread itself.
As general advice, don't simply add threads willy-nilly. You should know exactly which variables and data structures are shared between threads, where they are accessed, and why. And you should be keeping said sharing to the minimum.