... Perhaps a piece of wire or metal got lodged inside a PSU and touched a capacitor and the casing of the PSU?
Since the PSU casing is grounded, if this situation occurred, the most likely thing to happen would be a breaker would pop or perhaps the PSU would fail but it
shouldn't be possible for someone working on the computer to get shocked.
It really is a misnomer to say that current kills, not voltage. While it's true that current flow across the heart is what kills you, how much current flows is dependent upon the voltage and skin resistance. Skin resistance varies due to a number of factors such as whether wet or dry but the major contributing factor in electrocution is the voltage, the higher the voltage the more likely skin resistance will be overcome to allow sufficient current flow thru the heart.
The statement that a cellphone battery could kill you under the right conditions is true, but misleading, as the right conditions would have to be that the battery was connected to probes that pierced the skin on either side of the heart. That's about the only way the cellphone battery's low voltage could get enough current to flow to interrupt the heart.
Back in the 70s, I worked as a tech on huge power supplies that were capable of delivering 1000A @ 300V. I once got shocked by 480VDC thru my right arm from my elbow to my pinky finger. If that would have been from one hand to the other so that the current flow was across my chest, I wouldn't be here today. It hurt like he11 but I was able to continue working. Needless to say, I was a bit shaky the rest of the day.