Having dealt with both libraries a lot over the last few months, I can tell you there are some big differences, especially if you're dealing with large datasets. This blog post outlines just a few of the problems, and having dealt with LDAP instances containing over 500,000 entries, I can vouch for its accuracy.
The System.DirectoryServices
namespace uses a lot of ADSI and COM under the surface which can add a lot of overhead, particularly with disposing objects. The System.DirectoryServices.Protocols
interacts directly with the low level LDAP APIs, giving you much more control and much better interoperability with non-Microsoft directories.
If all you're trying to achieve is some quick and easy connectivity to an AD/ADAM/ADLDS instance for relatively simple operations, it might be worth sticking with that namespace - otherwise, I would strongly recommend you invest the time to learn the Protocols namespace. I found this MSDN article to be a huge help when I was learning originally - it covers pretty much everything you'll need to know.