Presumably the options are:
1. Replace one of the mixer showers with an electrically heated shower.
2. Install a vented hot water system, with the hot water cylinder (HWC) heated from an extra zone from the central heating. One shower off combi hot water, the other off a (pumped?) supply from the HWC.
3. Install an unvented hot water system, with perhaps both showers of the unvented cylinder (no pump needed) but the kitchen hot off the combi hot water.
I'd see the benefits and pitfalls as:
1. Electric shower:
1a. For:
Probably minimum disruption to existing system.
A source of hot water in the event of boiler breakdown.
1b. Against:
Extra wiring and (possibly additional) consumer unit.
Generally poor flow rate.
They don't tend to last all that long - in my experience you'd do well to get 5 years regular use out of one.
2. Vented hot water system:
2a For:
Relatively simple provided you've got the space for a HWC and a cold water storage cistern (CWSC) which need to be as far as possible above the HWC.
With an immersion heater fitted you've got a source of hot water if the boiler breaks down.
No need for an annual service.
If the water supply is interrupted you've got a store of hot and cold water.
Can be fitted by any competent plumber.
2b. Against
Installation could need a fair bit of extra pipe-work.
You'd probably need a shower pump to provide sufficient pressure to get a decent flow rate.
Space taken up by HWC and CWSC
3. Unvented hot water system:
3a. For:
If you've got the pressure and flow rate it gives you mains pressurised hot water everywhere without pumps.
No requirement for a CWSC
With an immersion heater fitted you've got a source of hot water if the boiler breaks down.
3b. Against:
Installation could need a fair bit of extra pipe-work, but probably not as much as vented hot water.
Space needed for HWC and a few ancillary bits.
Must be installed by a plumber / heating engineer with a current "G3" qualification, who should also notify your local building control department.
Needs an annual service.
My personal choice, in order of preference, would be the unvented hot water system, an electric shower, a vented hot water system. Your preference will probably be different, but if there is no airing cupboard space or loft, you could probably rule out the vented hot water system.
As a final thought, it might be possible to replace the boiler with one which has a store of hot water (a sort of hybrid combi with small unvented HWC). How suitable would depend on the length of showers taken. You might get two quick (5 minute?) showers off the store, but you almost certainly wouldn't get two 15 minute showers. Also depends on the flow rate and temperature of the showers.