Good you make this point Johno. The manual is indeed not helpful on this at all.
Let me explain more: With an Amp sim, you need two slots, meaning you have two stomps, left and right, each with its LED, that you can use in STOMP mode (note, Zoom uses in the manual the term "control switch" for what I prefer to call the stomps or stomp switches). The left stomp switch of the Amp sim (depending of your scroll state this may be the middle stomp of the 3, not necessarily the leftmot of the 3 stomps) then turns the Amp sim on or off and the 2nd right stomp switch of the Amp sim engages the so-called 'SOLO' function. 'SOLO' is described in the FX list manual part as "Sets the volume when the control switch is on". That should actually be described better by saying that only the right stomp switch of the two slot effect is meant. This all refers to the last parameter of every Amp sim, called SOLO and which gets a value between 1-9 (by default on 3). This is the boost level you can add to the amp in your signale chain, a boost that you can engage or disengage with a simple stomp during playing. Indeed neat as Johno states.
BTW, there is a similar, not at all obvious feature for other 2 slot effect units, again not at all described in the manual part called FX list: E.g. the BassGEQ is one of those (Bass "Graphical"
Equalizer). When using this effect, this feature is quite important to clearly understand. This effects knows two states: A and B. With the left stomp switch of the BassGEQ you control again whether the entire effect is actually on or off. However, with the 2nd right stomp of the BassGEQ you control which of the two settings you want to use. Both, the A and the B setting includes all parameters of the 7 frequency ranges you wish to eq, including the overall volume parameter of this effect unit. Meaning with the BassGEQ you have actually 3 settings available, either bypass the entire equalizer or then use it by using either the A or the B settings, the latter choice being controlled by the 2nd stomp of the effect.
Along similar lines, some single slot effects, e.g. the Bomber, have a parameter that allows to specify what the stomp switch, here the one and only stomp, is doing. This may be useful whenever an effect could be meaningfully used for more than simply on or off as this is the case for the Bomber. E.g. the Bomber: If in latching mode, the stomp switch works the usual way, i.e. it controls whether the effect is on or bypassed in the signal chain. However, there is also a trigger mode for the Bomber. Trigger mode for the Bomber means not your playing triggers a shot to go off, but your foot only. I use this in one song about a mafia boss being electrocuted causing x-mas trees being without power and where some gun shots triggered by my foot may trigger the imagination of some in the audience

, while I can play may bass normally

happily

.
Cheers,
Andreas flf