In my opinion, learning MVVM and ReactiveUI at the same time would be a bit to swallow, because you're actually learning four things: (1) WPF; (2) the MVVM pattern; (3) reactive programming in general; and (4) ReactiveUI specifically.
That said, one of the reasons I like ReactiveUI is that it allows you to start simple and grow. (I'm still mostly at simple, for what it's worth.) You can start by using ReactiveUI the same way that you would use any MVVM framework, and don't have to learn or even touch the reactive pieces of it at first. Just use the nice little shortcuts it provides: let your ViewModels inherit from ReactiveObject (or ReactiveValidatedObject if you need validations), use this.RaiseAndSetIfChanged() and perhaps an occasional this.WhenAny(), but otherwise don't bother with all the complicated stuff about observables - at least, until you're comfortable with WPF and MVVM.