You can think of the first (high order) bit of the CLA byte as part of the INS byte. The reason is that this is the proprietary bit, which means that the rest of the APDU is only compatible with the format of ISO 7816, but not defined by it.
Obviously it is better to try and find other methods than fingerprinting the APDU communications, although I must admit I could not find much on protocol identification in the ETSI standard you pointed to. There are many different smart card protocols and ISO 7816-4 is only a (very badly designed) umbrella protocol.
If you are lucky you will have some more information in ISO 7816-15, but most of the time only ID cards adhere to that particular part.