What type of GC separation are you performing?
If its based on boiling points (bp) you should select a STD which wont interfere with your analytes and is within the bp range of those analytes.
To be honest, I'm more familiar with the use of internal STDs (IS) in bioanalytical LC (or LC-MS) where the IS is either a stable isotope variant of the analyte or a compound of similar structure. In these situations, the primary function of the IS is to compensate for variations in extraction efficiency.