How old is your baby?
My supply also met my boy's demand nicely, he also fed very frequently. He's latched on for almost all his feeds. At any point, I could only store max 3 bottles of milk in freezer.
To stimulate supply, use the breastpump for about 5-10 minutes after a feed. Purpose is for stimulation, not to express milk yet.
After 6-8 weeks when supply stabilizes, then try to express for storage.
To let hubby feed, you can express milk at about 15-30 minutes before you think baby wants to feed. The milk would have probably come in by then. But in very early weeks or for some mums, expressing cannot match the volume of milk produced by latching on. So after the bottle-feed, might have to let baby continue latching to be satisfied.
To store, I could only wait until baby overslept (rarely). Or after he fed, try to express both sides. Usually, amount is little (10-20ml), so I add up a few times to get 1 bottle.
After 1-2 months, baby may also sleep longer. So you can wake up to express for storage and to stimulate supply.
And when hubby is feeding baby milk stored in fridge, you'd still need to express milk at about the same time, to avoid missing a feed. If missed, supply could drop or you could face engorgement. So actually, the breasts can't really take a break -- it's either feed directly or pump, according to baby's demand.
All the best!