I’m not sure those are the only two possibilities. And I hope somebody with more expertise into this particular charging system weighs in. But…
1. You put battery on charger overnight, and battery is fully charged.
2. You start the truck, pulling hundreds of amps in doing so. Battery is no longer fully charged.
3. The charging system either sees that latter fact or goes into an automatic “top off” mode, which you see as 14.5V*
4. In short order the battery is topped off again, so the charging system drops the voltage to 12.5V*
*in both these cases, I think you’re reading RMS voltage, but it is actually just the effect of the variance in PWM. PWM light dimmers don’t lower the voltage to the bulb, they just vary the “on time” of a set voltage, but the effect is virtually identical if the drain on the voltage acts like a filament or battery.
I would think that going to a dealer and having them check the charging system would be relatively cheap? Might give you peace of mind.