Don't both with your own XML operation, the AFNetworking operations and queue can provide all of the queue management you require.
To keep things tidy, put your XML parsing into a number of methods (either in the controller class or a/several helper classes if you wish). Then you can call these methods as appropriate from the AFNetworking success blocks.
Be sure to set the maximum concurrent count on the queue if you're going to add 20 operations so you don't flood the network with requests.