There's nothing available directly from within the managed libraries. You'll need to use P/Invoke to call into the native Coredll.dll
and use a method called GetSystemInfo.
pinvoke.net is an excellent resource for using P/Invokes for both mobile and desktop development. The pertinent entry for you is:
http://www.pinvoke.net/default.aspx/coredll.GetSystemInfo
Calling this method will return a SYSTEM_INFO structure that contains information about the processor architecture.
If that route looks like too much work, you can always check out a commercial package called Smart Device Framework from OpenNETCF:
http://opennetcf.com/Products/SmartDeviceFramework/tabid/65/Default.aspx
In the SDF, you'll be interested in OpenNETCF.WindowsCE.DeviceManagement.SystemInformation
-- that will return the same basic information as the P/Invoke, but within a nice managed wrapper.