Second question first, yes ESSM is quad packed, so for example in both the Anzac's and FFG's the 8 cell Mk 41 can carry a load of 32 ESSM, and I suppose in theory the Hobart AWD's with their 48 cells could carry 192 ESSM, but the questions is, why would they carry that load?
With their primarily role, eg, Air Warfare, I would imagine the balance would be way more in favour of SM-2 (and eventually replaced by SM-6), why would you want to carry such a large load of ESSM at the expense of SM-2/6?
The other factor in the future will be the introduction of land attack cruise missiles, which will no doubt reduce the SM-2/6 load even further.
Going one step further in the future, if LRASM-A is introduced, (would it replace or supplement Harpoon?) there is another missile that would be fired from the MK41 VLS, those 48 cells are starting to get pretty crowded with that mix.
Maybe if there was room somewhere else, say over the hangar, it might be worth putting an 8 cell VLS for ESSM to free up space for the possible load of SM-2/6, Cruise missiles and LRASM-A, is that possible?.
Back to your first question, I might be wrong, but I can't see a VLS system being installed in the Canberra's, I would imagine that if the LHD's were going into a hot situation that a couple of Phalanx, out of the RAN's pool, would be added and that their escorts would be loaded up with ESSM and SM2/6 and if it was a 'really' hot situation, they would probably be part of a larger US led coalition including USN carriers, cruisers and AWD's.