Hi,
Since you are using LabVIEW and a DAQ board, this question probably should have gone to either the DAQ or LabVIEW board.
However, since I'm here I'll help you out with this one.
You should start with one of the shipping examples in LabVIEW. Under Help go to Find Examples >> Hardware Input and Output >> DAQmx >> Analog Generation >> Voltage >> Gen Voltage Update.vi
This example program will update a constant voltage to a single channel. You will need to modify it to do multiple channels. Go to the block diagram (Ctrl + E) and take a look at the DAQmxWrite VI. You'll see that it is for 1Chan 1Samp. You can click on the VI to make it for Multiple Channels. You'll find that you will need to make the output data an array since you will be doing multiple channels.
Then in the front panel you can specify multiple physical channels in a couple ways:
Dev1\ao0:1
or
Dev1\ao0, Dev1\ao2, Dev1\ao4
The number of data values in the array that you are wiring to the DAQmxWrite VI should match the number of physical channels you specified.
See the attached file.
-Sal