The individual jacks are intended to be used one at a time.
- If you have one 8 ohm cab use the 8 ohm jack
- If you have one 4 ohm cab, use the 4 ohm jack.
- If you have two 8 ohm cabs, connected them in parallel to the 4 ohm jack.
Can you run a 4 ohm and 8 ohm cab? Well yes, but it's an impedance mismatch, which is harder on the amp. I believe Ampeg's official word is
don't do it.
At the very least an impedance mismatch will reduce how much power the amp can make and increase wear and tear on the tubes and components. At worst the amp could be damaged.
Many tube amps can tolerate a minor impedance mismatch. Some amps are okay with a 2:1 or 1:2 mismatch. Some are safer if the impedance is higher than expected, some are safer if the impedance is lower than expected. Some amps should not be used with an impedance mismatch.
I recommend showing the amp the expected load. I believe the V4B is relatively safe at 2.67 ohms, but I don't know if you should use the 4 ohm tap or the 2 ohm tap. Choosing to run an mismatch means you accept increased risk to the amp...I.E. if the amp blows up it's on you. My advice is determine which tap to use, and only do so if you have an emergency.
@beans-on-toast explains here and recommends using the 4 ohm tap:
2013 Ampeg V-4B 100W Reissue Pt2
Then he recommends the 2 ohm tap here:
Ampeg V4B 212AV+210AV (2.67ohms)
Perhaps beans will comment regarding the change in advice.