DNA barcoding is a technique in Molecular Biology that allows you to identify a plant species (hopefully, but sometimes genus only) by simply isolating a small fragment of their DNA. As you may know, different genes are subject to a different mutation rates which means that different part of the genome (or different genes) may differ a lot or not at all between different species. By targeting some of the most variable gene region, you can have a sequence of DNA that is always different between different species but still the same between individuals of the same species. For insects, for example, the most used DNA barcode region is COI, and there are entire database storing this gene region allowing you to compare your sequences with those already indexed. For plants, ITS is used quite a lot.
Chemotype identification is a similar process but based on the most abundant chemical produced by the plant. Different plant can produce different chemical, despite having morphologically similar phenotypes.
In short, both DNA barcoding and Chemotype identification are two techniques that may allow you to distinguish different species of plant (or animals, or fungi) even when you would not notice morphological variation between them because they look extremely similar (cryptic variation).