Yes, the principles of the Win32 API are useful to learn - these principles are the foundation on which everything else is built.
The .NET APIs for GUI development, both Windows.Forms and WPF, do what they do within the constraints of what is possible on top of the Win32 API. Key architectural decisions of these frameworks were constrained and informed by the Win32 API.
On the other hand, you are less likely to get a lot of value from diving deep into the API, as there is a lot to learn, and given that you spend most of your time working in C#, you'll have less opportunity to use the knowledge directly.
BTW, the same applies to other technologies as well - like networking, cryptography and hardware design. Learning the fundamentals will help you become a better developer.