Sadly, no, every user will not be able to access other user content on both consoles.
I am also in this case, and you can't play the digital content of another account unless the Nintendo Switch is the primary console on this account.
Let's say that on your Console1, there are User1 and User2, both have digital content linked to their accounts. For this example, User1 has Pokémon Let's Go Eevee and User2 have Diablo 3 (yup, it is my case).
As it is now, each user can play both Pokémon and Diablo.
Now, you buy your Console2. You move User2 data to Console2 and make this console his primary one.
As it is after this, for each console :
- On Console1, User1 and User2 can both play Pokémon as it is User1 primary console, but only User2 can play Diablo if the console is online.
- On Console2, User1 and User2 can both play Diablo as it is User2 primary console, but only User1 can play Pokémon if the console is online.
This Nintendo website page about digital content also supports this (emphasis mine) :
- You can purchase downloadable software on the Nintendo eShop from any Nintendo Switch console associated with your Nintendo Account.
- The first Nintendo Switch console you use to connect to Nintendo eShop on Nintendo Switch will become the primary console for your Nintendo Account.
- A Nintendo Account can have one primary console, and while using the primary console, any user account on the console can play the digital software you've purchased.
- You can use your Nintendo Account to play your digital games on non-primary Nintendo Switch consoles, but the Nintendo Switch console must be connected online and other users on that console will not be able to play those games.
- If you have an active membership, save data (for supported digital AND physical games) can be shared between consoles using the Save Data Cloud Backup feature of Nintendo Switch Online.