Hello,
The difference of +-5mV is ok when you're using 3.2VDC as input. NI has an "Accuracy Calculator" on the web where you can check how precise your DAQ Setup should be. I entered you're values and I received a total system accuracy of about +/- 20mV. You see, that you're in this range.
You'll find the accuracy calculator here: http://www.ni.com/advisor/accuracy/
Hope this helps.
Luca
Regards,
Luca