Ohm's Law
always applies in these situations.
Any voltage/current source looks like a perfect voltage source with an internal resistance.
The 240 volt mains supply has a very low internal resistance,so can source a great deal of current .
If you are across the mains,the circuit consists of V( supp) which is the perfect source, in series with R( int) & R (you).
In the Mains case R(int) is sufficiently low that it can be ignored, so the total current is very close to I= V(supp)/R (you)!!
For 240 volts,that is effectively 240/R(you).
In most really high voltage power supplies that Electronics people play with,R(int) is no longer negligible,so any attempt to draw enough current to kill you causes the output terminal voltage to fall to a low value,limiting the possible current.
It will still "bite" though!
WARNING! WARNING! Will Robinson!! (1)Large capacitors may be charged to high voltages in some circuitry.
The internal resistance of capacitors is very low,so they can deliver a dangerous shock,both when the device is operating,& immediately after turn off!!!(2)My comments about high voltage power supplies earlier,DO NOT apply to the power supplies commonly used for tube type Radio RF Power Amplifiers.
These may be intended to supply 2kV or more,at several Amps to a power Vacuum tube.
To do this,they need a very low value of R (int).
From our above discussion,you can see where that leaves you!