The culprit was this setting in Group Policy:
Microsoft Office 2010/Global Options/Customize: Disable UI extending from documents and templates: Enabled
This policy setting controls whether Office 2010 applications load any custom user interface (UI) code included with a document or template. Office 2010 allows developers to extend the UI with customization code that is included in a document or template. If you enable this policy setting, Office 2010 applications cannot load any UI customization code included with documents and templates. If you disable or do not configure this policy setting, Office 2010 applications load any UI customization code included with a document or template when opening it.
It would appear that this setting was, as described, preventing our customisation of the ribbon from loading. No error was being provided (not sure if one could be expected in the circumstances), and this isn't an option that is visible in Words options screens.