So, being new to this stuff then....

I have an Ibanez S520, Peavey Rage158 and Zoom G2.1u....

Where do I start to adjust tone settings.

Guitar tone knob....?
Amp tone knobs....?
Zoom G2.1u EQ settings....?
Zoom G2.1u tone settings....?

It is a little bit of a mystery to me as to where to start with setting things up. Maybe there is no right or wrong but is there a best method of attack?

I usually flatten my eq and set everything else at 12 o'clock go from there.
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Sorry, for clarification do you mean everywhere? On the amp, guitar and pedal? Once that is done what is the first part that you adjust, amp end, pedal or guitar? Where do you move to next? Sorry - just looking for some specific guidance on the matter

Thanks for getting involved!
I think he meant the controls on the amp. Setting the amp tone controls at the half way mark is a good starting point, as you can listen to the tone and hear if you need less or more of any particular range of frequency content and have plenty of adjustment range in both directions from where you started.

Once I've got everything set to half way on the amp I then adjust the tone settings on the guitar before fine-tuning the amp settings to the environment that I'm playing in, but some people skip this step and leave the guitar controls on 10 all the time and that works for them. Usually pedal settings are adjusted last as generally you need to set the pedal up to work best with the base tone you're getting from the guitar and amp in order to get the best results.

That said, there's not really any right or wrong way to do this, nor is there any 'best' method - it's simply part of the learning experience
I like analogue Solid State amps that make no effort to be "tube-like", and I'm proud of it...

...A little too proud, to be honest.
Blompcube We got a winner... I said, we got a winner! Perfect. thanks for that - just the answer I have been looking for. Thanks for the advice. Will get stuck into it.