I think I would not go POX ever again. If you write WCF so that the service itself is independent of the binding and binding is done in configuration files, then WCF is pretty much agnostic about transport and protocol. It can do SOAP, JSON, REST, or its own form of binary serialization. All of this is in the binding. Internally, WCF only specifies what gets exposed in terms of operation and data contracts (all defined by class, method, and property attributes). WCF gives you tremendous flexibility in this regard, with more to come in 2010.
From the Silverlight side, WCF requires that you write some plumbing code. The .NET frameowrk has the tools to build the proxy in your Silverlight project, but you must be prepared to handle all WCF responses asynchronously, and the proxy cannot catch exceptions thrown by the service.
.NET RIA Services hides all this. It uses WCF under the covers, but that is completely hidden. You don't have to write asynchronous code. You define validation once, mostly declaratively, and it works both server-side and client-side. Release 1 will be targeted for Silverlight, so you don't get the versatility to use the service elsewhere. That scope is supposed to be broadened in later releases.
I don't know enough about ADO.NET Data Services to compare. I suspect the answer would depend on whether you want to expose your data to more than just Silverlight usage.
.NET RIA Services looks like the direction I'd want to go (looking at these issues myself, with a large application in mind). The big issues for me will be implementing a very large collection of functionality in the service layer, and not being able to code directly to the data access layer (we have to be able to run on either SQL Server or Oracle).
Using WPF instead of Silverlight changes everything, depending on where your data resides. It's like the old question of Winforms vs. ASP.NET. With WPF, you're building a Windows client app, and you don't need to use any form of service-based data interface at all, unless your data access forces you into it. You'll still want to separate data and business from presentation code, using MVVM, MVC, or MVP. Other than that, you have the option to treat data access as a layer, rather than a wholy independent tier.