The Maypole documentation is arranged over several files; this is a good one to start with.
Once you've read this, you should probably look at About.pod, the guide to what Maypole is and how the Maypole request works. It also describes how to set up a simple CRUD web application in Maypole.
The next two chapters are quite thorough, and you might want to skip over them if you already know how Class::DBI and the Template toolkit work. Model.pod and View.pod describe these technologies and their relationship to Maypole.
Now we present the default actions and templates - the factory templates - in StandardTemplates.pod. When you have read these chapters, you are ready to start building more complex applications in Maypole than just a simple CRUD interface. Beer.pod reintroduces the beer database application and shows how to move from the "magic" of the automatically supplied templates and actions to a customized application with user-specified actions.
Request.pod contains more information about the Maypole request object and provides some cookbook-style techniques: how to provide authentication, how to provide a REST interface, how to override various stages of the content generation process, and so on.
The final chapters are examples of how to construct large web applications in Maypole: Flox.pod describes a "social network" site similar to Friendster and Orkut; PetStore.pod implements the Java/C# benchmark Pet Store application; and BuySpy.pod implements the ASP.NET sample portal application.