I had a difficult time trying to use this property to get rid of some content types from the New button. I finally figured it out with the following code. It works like a charm.
Dim newListItem As SPListItem
Dim newFolder As SPFolder
newListItem = spList.Folders.Add("", SPFileSystemObjectType.Folder, folderName)
newListItem("ContentType") = "Attribute"
newListItem("Title") = value
newListItem("NumberOfLevels") = levels
newListItem.Update()
newFolder = newListItem.Folder
Dim contenttypes As New List(Of SPContentType)
contenttypes.Add(spList.ContentTypes("Valid Value"))
newFolder.UniqueContentTypeOrder = contenttypes
newFolder.Update()
Badically, create a new list of SPContentTypes, add a content type from the ContentTypes property of the list and then assign that to UniqueContentTypeOrder.