The answer depends on what you consider as your system.
One system
If your system contains both the webservice and windows service as parts of your (multi-tiered) system, then neither is an actor. The functionality offered by the windows service will be one (or more, depending on the complexity of the service) use case. If you assume that webservice it might become a second use case, that is included by the windows service (a rare case but works here).
The mere fact that those parts are on separate machined doesn't change a thing. It's common approach that database has it's separate machines but no-one reasonable consider it to be separate from the system itself.
Two systems
If you treat windows service as a separate system then you will actually have two use case diagrams, one for each of the systems.
In this case the use case diagram of windows service will have the client as a primary actor and system containing the webservice as a secondary actor.
In the use case diagram of the system with webservice your primary actor would be the windows service system (again as a whole , not a service itself). In this diagram the client is not depicted at all as it does not interact with the system.
Component as a system
Even if you consider both windows service and webservice as a single system, you may still depict use cases of components rather than the system as a whole. In such case the aproach will be similar to the situation with two systems.