Having good QOS and adequate network segmentation are the 2 biggest factors. QOS has to be conistent across your entire network.
As for measuring performance, I have seen some 3rd party apps out there such as NetQOS that supposedly do this. I am not sure how well they work, but they look promising in demos.
Generally if you are having issues with congestion, etc. having VOIP will bring them to light as VOIP is more sensitive than data traffic.