I think it depends on the person (obviously this is already a well established thought haha). Say with mushrooms - if you're undergoing the experience for a spiritual reason, the source of the 4-HO-DMT (psilocin) may play a part in your mindset. You may be getting back to nature so to speak, ergo it may feel more 'right' to obtain the active compound from its natural source - the mushroom - even if you somehow hypothetically had access to pure lab-synthesised 4-HO-DMT. However for the more recreational tripper, or simply someone not chasing that particular therapeutic state of mind, the source of the compound may be entirely irrelevant and of little concern; hell, you may even prefer a pure lab-synthesised version over the naturally occurring one as it removes the need to eat the physical mushroom.
But this is most certainly a matter of opinion and personal preference, which simply cannot be argued as to which one is "better". The only circumstance in which it could would be related to my last point above: it would be easier on the stomach and digestive system to consume an amount of pure 4-HO-DMT than it would be to consume the amount of mushrooms (dried or not) required to provide an equal amount of active compound.
But this is most certainly a matter of opinion and personal preference, which simply cannot be argued as to which one is "better". The only circumstance in which it could would be related to my last point above: it would be easier on the stomach and digestive system to consume an amount of pure 4-HO-DMT than it would be to consume the amount of mushrooms (dried or not) required to provide an equal amount of active compound.