The PC maker has no control over what devices may be plugged into the audio output, so takes the sensible precaution of not having any voltages on it, other than the audio output signal.
If you put your probe on "backwards" (with the "ground clip" on the non -grounded output), the most likely outcome is that you won't see anything.*
With a desktop, it will probably short circuit the audio amplifier output, but it will most probably survive this OK, although you shouldn't make a habit of it!
Again, with a desktop, you can probably tell which wire is which by not connecting your ground clip at all to the wires, but pick up a point of the back of the PC where there are often metal panels, or connectors with metal outer shells, & connect it there.
*A laptop will normally not have a direct ground connection, but it depends on whether you have any other devices connected to it.
Hams plug stuff into the audio inputs & outputs of their PCs all the time when they want to use the various "digital modes" in their transmission & reception, with very few problems.