Tony, in each case I think you have to do your local research.
Out here the highest octane gas is the leaded 100 octane aviation fuel. (not legal on the road because we pay road tax when buying fuel)
The next highest and road legal is a 98 octane ethanol blend. then there are fuels that run around 95 octane, high in aromatics, but no ethanol (my choice) the lowest octane rating available here is 91 and is the most used fuel here. Interestingly the handbooks for my various two stroke implements (world famous and orange coloured) suggest using the higher octane fuel (95) because it has less impurities in it.
These variations come from locally blended and imported fuels (international companies and local companies)
Of course your local fuel suppliers will deliver an entirely different set of specs to the market.
Essentially the Octane rating is the "anti knock" value of the fuel.
My understanding is that a high octane rating means the fuel burns slower. (the flame front travels slower from the point of ignition through the fuel mix in the combustion chamber) This is of little consequence in a flattie that was built to use fuel of about 68 octane and had a compression ratio of about 6:1. Today's fuel has you well covered here.
In a High compression engine say 11:1 the conditions are such that the flame front will travel through the fuel air mix so fast that it would cause catastrophic damage. The "anti knock" additive in the fuel stops this. The "anti knock" additive translates into the Octane rating.
My disclaimer: You should try to stick with one spec (of fuel) and adjust your timing (vacuum brake) accordingly. (You probably wouldn't notice the difference)