You would need first to learn how to use Brainstorm in general. Follow all the introduction tutorials at least until #19, using the example dataset provided:
https://neuroimage.usc.edu/brainstorm/Tutorials
Then you could read this advanced tutorial that deals more specifically with EEG:
https://neuroimage.usc.edu/brainstorm/Tutorials/Epilepsy
Finally, you will need to find a way to import your recordings into Brainstorm. I don't know what file formats you can export your data to. The list of supported file formats is available here:
https://neuroimage.usc.edu/brainstorm/Introduction#Supported_file_formats
When you have your recordings in the database, it will be very straightforward to compute PLV between pairs of signals.
If you don't want to go through all this training, you could try to reuse directly parts of the Matlab scripts for the PLV computation: