Wow, great advice all, thank you.
So for further information the house walls & floor are currently completely uninsulated. Double brick leaf with thin cavity & outside render. Loft is insulated with fibreglass. Concrete slab floor (unknown depth) with thin screed.
On the plus side (as PeterW & Iceverge mentioned) the building has a tremendous thermal mass. On the negative side retrofitting insulation is going to be tricky. After looking at options any additional insulation will need to be external unfortunately; the initial thought is to insulate by extension over the coming years, then externally insulate whatever is left over.
Because of this, as you mention, the estimated heating load is high. However even in winter the building is retaining heat well over several days; I suspect the base U-value isn't telling the full story here. Trying to spec the heating system for the worst case scenario.
The thermal storage company I contacted responded to some figures about sizing the thermal store with "we're not heat engineers", so my current thought is to follow your advice and go for two separate unvented cylinders.
My main thought with setting out was to keep this simple; two cylinders definitely does that.
My main concern about ASHP was installation cost, unit lifetime, and therefore payback period. I'll make sure the cylinders have a redundant loop/coil that can fit one, and then run the sums again once everything else is up and running.
ProDave; as far as I'm aware there is only one tariff like this. Average peak price per kWh (between 4pm and 8pm) over the past year is 20p/kWh to 25p/kWh. Overnight prices 5-6p/kWh, rest of the day prices 8-10p/kWh. Varies by region.