Actually what you just described is very common scenario.
In well established tank, unless well monitored, pH will begin to drop when water's buffering ability diminishes. Every tank is different as its bioload is different.
When pH goes lower than what you have described (maybe even lowered than 6.0 as you mentioned and i believe that), your nitrifying bacteria seems to be disturbed/deactivated thus no activities to oxidize
NH3 (ammonia) to
NO2 (nitrite). When pH is low enough, NH3 will increase but DON'T be ALRMED since any NH3 at such low pH is harrmless since in nontoxic form NH4+ (ammonium ion).
Have seen people cause more death when one find such low pH by adding bicarbonate ion (Baking Soda) without checking NH3.
As pH is increased, more NH3 will be shifted to toxic NH3 form.
What I would recommend is simple small (20-25%)
water change, as needed, to keep NH3 low (but not zero via water change) and as water changes (pH of new water should be lot higher than tank water; my tap is around 7.0) are done, pH will rise to a point (even just slightly above 6.0)where nitrifyfication will resume thus NH3 will go down to zero on its own. Then stop water changes other than routine maintenance. When thing are all stablized (no NH3, NO2) then could/should GRADUALLY raise pH to desired level by method you are used to.
Once pH is at desired level, could add
buffer to stablize the pH. Even this buffer will exhaust as time goes by thus need to figure out the time frame (how long before ph plunges, etc) on your tank thru testing and logging. You should be able to derived the pretty accurate time frame when to raise pH and/or buffer provided nothing is changed. (additional fish, less routine/regular maintenances, amt of food, etc)
As far as why pH drops, Any protein matter will breakdown to its building block, Amino Acids, Some CO2 in water is in Carbonic Acid, urine as in Uric Acid, Some nitrate in nitric acid, etc, etc, etc. Unless counter acted by buffer, will eventually drop once buffering ability drops.
No assuming on NH3, NO2,
NO3, or pH! Actual test will eliminate lot of guessing thus less chances of having problem with fish, IMHO
Hope this help out a bit.