Gave some further thought to this, and here is another approach you may want to consider.  If you're not interested in a catalog of previous IDs, then you could simply use a custom document property to store the last ID that was used.  
In Word 97-2003, you can add a custom property by going to "File / Properties", choosing the custom tab and assigning a name and value there.  Adding a custom document property in Word 2007 is a bit more buried and off the top of my head, I think it's "Office Button / Prepare / Document Properties", choose the little drop down box for advanced properties and you'll get the same ol' pre-2007 dialog.  
In the example below, I called mine simply "DocumentID" and assigned it an initial value of zero.  
The relevant bit of code to update a Custom document property is:
ThisDocument.CustomDocumentProperties("DocumentID").Value = NewValue
As a proof of concept, I created a .dot file and used the following code in the Document_New() event: 
Sub UpdateTemplate()
    Dim Template    As Word.Document
    Dim NewDoc      As Word.Document
    Dim DocumentID  As DocumentProperty
    Dim LastID      As Integer
    Dim NewID       As Integer
    'Get a reference to the newly created document
    Set NewDoc = ActiveDocument
    'Open the template file
    Set Template = Application.Documents.Open("C:\Doc1.dot")
    'Get the custom document property
    Set DocumentID = Template.CustomDocumentProperties("DocumentID")
    'Get the current ID
    LastID = DocumentID.Value
    'Use any method you need for determining a new value
    NewID = LastID + 1
    'Update and close the template
    Application.DisplayAlerts = wdAlertsNone
    DocumentID.Value = NewID
    Template.Saved = False
    Template.Save
    Template.Close
    'Remove references to the template
    NewDoc.AttachedTemplate = NormalTemplate
    'Add your ID to the document somewhere
    NewDoc.Range.InsertAfter ("The documentID for this document is " & NewID)
    NewDoc.CustomDocumentProperties("DocumentID").Value = NewID
End Sub
Good luck!