- If you're going WCF, the WCF REST Starter Kit that JP referred to is a great place to start.
- Omar Al Zabir provides a pretty good example of using ASP.NET MVC to provide RESTful services that are fluent in both XML and JSON
- You can also go the ADO.NET Data Services route you suggested. These services are built on top of the WCF stack.
I've never stumbled across any really good guidance on how to select between these options. In ASP.NET MVC you take on the majority of the plumbing burden but also have maximal control. Straight RESTful WCF is the happy middle ground although WCF tends to want to have things done its way. ADO.NET Data Services are pretty magical with the downside of buying fully into a given approach to generating these services and losing more flexibility.
There are a couple of good books you can read on the topic of RESTful services with .NET. Both O'Reilly and Microsoft Press have recently released books on this topic. Perhaps the most important advice I can provide you is to consume and understand several open RESTful services (e.g. Twitter, Amazon, Flickr) to understand the design decisions that went into creating the services. User provisioning, authentication mechanism, and supported content types (e.g. JSON, XML, RSS/ATOM) are some of the decisions that you can observe in action to aid you in your path to creating your service API.