Mark,
For two people a properly installed large combination boiler would work fine - on a personal basis for a large house I would still go the system / unvented route.
To compare quotes, be sure you know exactly what is being installed. Where it is going to go. What pipework is going to be different from the current installation and is it going to be visible. Where is the flu going and again how much is going to be visible. If the boiler / flue is being relocated is the brick / stonework to the exterior wall going to be properly matched? Is the inside wall going to be properly replastered if left visible.
A walk through the house with the person who is physically going to undertake the installation is often very productive (on both sides) - the key for getting a good neat installation is combing through the detail. Particularly, if the boiler is going into an existing fitted kitchen. A large combi is a bulky item and has a lot of pipe work feeding in and out ( and sometimes exposed external filters ) - once installed they don’t quite look the same as the hidden pipework versions shown in the brochures!
Talk through the new control system, where is it going to be placed, is it wireless, is it easy to operate. For a large house with only two occupants, zoning is important - to optimise energy useage. An Evohome type system may be appropriate where each room can be individually zoned.
Talk through your existing heating and hot water system, are you happy with it, any problems you experience, noise, any cool spots, radiators that never seem to do the job properly etc. Now is the time to rectify any issues.
Are you happy with your current cold water pressure and flow? Is it adequate for the proposed large combi? - I do a lot of work in Knutsford, the incoming water pressure there is dreadful!
Ask him / her how long is the installation going to take (how many people).
Most good plumbers want to deliver a quality job that you will be pleased with, to do that they need to know what is important to you. I have a few customers who do not want to see any exposed pipe runs - so for them I always quote with the option for fully concealed pipework, I generally get the work.
Thereafter, you will start to get a better feel on the value of the offers you have received and exactly what you can expect both visually and performance wise from the new system.
Hope this helps