Nope. Remember. DC is direct current. That is a fixed (hopefully) voltage that you measure using the DC scale on the DMM.
A guitar signal is a complex AC signal. It varies in amplitude and also contains harmonic frequencies. A DMM set to AC scale will show a digital reading that moves around and never settles to a fixed value. This is best observed on an oscilloscope.
The best way to determine if the clipping diodes are working is to use your ears and hear the difference in tonal quality as you switch from one setting to another. Remember, clipping may not commence until the signal level exceeds a threshold level.
I hope this helps.