Using one of the PFI lines is actually a great idea.
For analog input, you could try the LabVIEW example VI, "Acq&Graph Voltage-Int Clk-Dig Start" you'll be able to get up and running quickly. You may select which line to trigger from using the controls under "Trigger Parameters".
If you are performing analog output, the "Gen Mult Updates-Int Clk-Dig Start" works in a similar way.