Here is the Dev Center site of Microsoft. You can find dev information about Desktop, Hardware, Web etc.
.NET Windows Presentation Foundation (WPF): This is the preferred technology for Windows-based desktop applications that require UI complexity, styles customization, and graphics-intensive scenarios for the desktop. WPF also takes advantage of XAML views. You can leverage the new simplified asynchronous capabilities (async/await) in .NET 4.5. WPF development skills are similar to Windows Store development skills, so migration from WPF to Windows Store apps is easier than migration from Windows Forms.
.NET Windows Forms: .This was the first UI technology in the .NET Framework for building desktop applications. It is still a good fit for many business desktop applications. Windows Forms is easier to use and lighter weight than WPF for simple scenarios. Windows Forms does not use XAML, so deciding later to extend your application to Windows Phone or Windows Store entails a complete re-write of your UI.
For business application technology guide, you can download from here.