If your signal is of single tone or multitone, you can use the Extract Single Tone Information or Extract Multi Tone Information VI respectively. The VIs will estimate the PSD and find the peak(s) automatically.
You also can estimate the PSD by yourself and then call the Peak Detector VI to find the peaks. You can find the Peak Detector VI on the Signal Processing>>Signal Operation palette. If you have LabVIEW Advanced Signal Processing Toolkit, you can use the WA Multiscale Peak Detection VI to find the peaks, which is more robust.