If you have a hot sauce extract containing nordihydrocapsaicin, capsaicin, dihydrocapsaicin, and homodihydrocapsaicin, the Cogent Bidentate C18 2.o™ HPLC column is a good choice for sufficient separation when the compounds are analyzed by LC-MS; look for the [M+H]+ ions.
The following gradient should be a good starting point:
You may get EICs which look like this:
1. nordihydrocapsaicin, 294.2064 m/z [M+H]+
2. capsaicin, 306.2064 m/z [M+H]+
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4. homodihydrocapsaicin, 322.2377 m/z [M+H]+
For peaks 1 and 2, you will be able to obtain separate peaks for each compound in the EICs so there will not be an issue of interference from co-elution.
In terms of sample preparation, try using a Soxhlet extraction procedure.