The best thing would be to do a headspace sampling of the volatiles from (intact) plants followed by a (GC and) GC-MS analysis. This could be done either by static or dynamic sampling techniques. This in practice means that you collect the atmosphere that is rich in, preferably saturated with, the plant volatiles and inject it into a GC-MS. For this you need your GC-MS to be equipped with a headspace sampler and that the injection port, liner, etc are appropriate for that (large volume injections, valves...).
The other possibility is to use an SPME (solid phase microextraction) fiber for the collection of volatiles. You have to take care of the choice of the fiber polarity not to miss out on some of the volatiles. The analysis is done by exposing the completely desorbed fiber to the headspace of the plant in a closed vessel for a period of time (with or without heating if the vessel) and them placing the fiber in a specially designed injection liner for the desorption of the volatiles and injection into the GC-MS system.
Thus, it depends on what you have available in you institution.
In the end, if all of the above is not possible for you, you could do a solvent extraction with a mixture of pentane and diethyl ether (both highly volatile to ensure you loose as little as possible of your precious plant volatiles).
If you have any questions, or would like me to send you publications that deal with this subject, just ask.
It all depends what you want to extract volatile substances. There is no single golden mean for all compounds and various raw materials. That's the question we ask ourselves every time when you want to explore new material. The best way is the method of testing for raw materials, so use all available, as each of them will reveal you a different face of the raw material. Greetings.
If your compounds are highly volatile, you can try cold extraction with solvents but the trouble is isolation of these compounds from the rest of the compounds extracted by the solvents. Head space analysis of course helps to identify these compounds.