You need state machines whenever you have to release your thread before you have completed your operation.
Since web services are often not statefull, you don't usually see this in web services--you re-arrange your URL so that each URL corresponds to a single path through the code.
I guess another way to think about it could be that every web server is a FSM where the state information is kept in the URL.
You often see it when processing input. You have to release your thread before the input has all been completed, so you set a flag saying "input in progress" or something like that. When done you set the flag to "awaiting input". That flag is your state monitor.
More often than not, a FSM is implemented as a switch statement that switches on a variable. Each case is a different state. At the end of the case, you may set the state to a new value. You've almost certainly seen this somewhere.
The nice thing about a FSM is that you can make the state a part of your data rather than your code. Imagine that you need to fill out 1000 items in the database. The incoming data will address one of the 1000 items, but you generally don't have enough data to complete the operation.
Without an FSM you might have hundreds of threads waiting around for the rest of the data so they can complete processing and write the results to the DB. With a FSM, you write the state to the DB, then exit your thread. Next time you can check the incoming data, read the state from the thread and that should give you enough info to determine what code to run.
Nearly every FSM operation COULD be done by dedicating a thread to it, but probably not as well (The complexity multiplies based on number of states, whereas with a state machine the rise in complexity is more linear). Also, there are some conceptual design issues--examining your code at the state level is in some cases much easier than examining it at the line of code level.