A good rule of thumb is that the RMS voltage of an AC signal can be approximately compared to the the DC voltage. This works perfect with pure resistive circuits, but if safety alone is your concern it will work with any other circuit.
The switch is rated at said voltage because this is the maximum permissible voltage across it when open. This is the maximum permissible voltage across the air gap before miniature lightning occurs. In theory, when closed, there is no voltage across it.
RMS voltage stands for "root-mean-square". You don't need to know what a "root", a "mean", or a "square" is to understand the calculation of this.
Formulas below are applicable to sinusoidal AC signals (the default). Any other waveform will be more complicated.
In terms of mid-line to peak of an AC signal (Vamp, the amplitude), Vrms = Vamp/sqrt(2).
In terms of peak to peak of an AC signal (Vpp), Vrms = Vpp/(2*sqrt(2)).
Just solve for Vamp or Vpp, which ever is of interest to you.
Frequency should not be an issue, as long as it is reasonably low.