With either technique, GC or HPLC, it helps to know the compounds you are trying to quantitate or identify. And there are many variable that can affect both techniques.
GC (gas chromatography) is generally good at separating volatile compounds. Identifying the exact structure can be difficult with standard detectors (say an FID or TCD). You need to get an instrument like a GC/MS for that.
With HPLC, the compounds can be separated whether they are volatile or not. The problem, again, is identifying them. Depending on the system, you can use the UV/VIS spectrum of the compound (say with a diode array detector) to narrow the possible compounds.
In both cases, sample prep, columns, and other related conditions can make a major difference.