To produce an voltage signal with your PCI-MIO-16E-4 you need to perform an analog output operation. For example programs go to NI Developer Zone >> Development Library >> Measurement Hardware >> Analog Input/Output >> Analog Output. The Continuous Waveform category offers the most flexibility in programming code.
For your hardware connection, all you need is to connect your DAQ board to a 68-pin terminal block with a 68-pin DAQ cable. To find out what cable and terminal block would best suit your application, please contact your NI sales representative.
Good luck with your application.