It looks like your form is set up to use the the 2007 InfoPath object model, which requires different objects to access the data source than what you have there.
Please try
MainDataSource.CreateNavigator().SelectSingleNode("/Sign/DocGUID").SetValue(Guid.NewGuid().ToString());
But that XPath looks a little fishy to me. Please try:
MainDataSource.CreateNavigator().SelectSingleNode("/my:Sign/my:DocGUID", NamespaceManager).SetValue(Guid.NewGuid().ToString());
Or
MainDataSource.CreateNavigator().SelectSingleNode("/my:myFields/my:Sign/my:DocGUID", NamespaceManager).SetValue(Guid.NewGuid().ToString());
If the first one doesn't work.