Hi,
I've looked at this before over 20 years, and these days frankly, I'd just buy a UK-specific connected commercial thermostat with local support.
There are a load of complications such as pump overrun-timers (dumb boilers don't control pumps efficiently), limits on boiler cycling (could be a max of 6x per hour for a gas boiler), modulation (if supported, this makes your boiler much more efficient), frost protection if HA dies, and the cost-engineering of a Y-plan system means it is far from logical (although John Ward does do a good job of explaining it).
Shelly is a good choice for many automation tasks and it has replaced Sonoff+Tasmota for many of my automation tasks. Getting sensors into a Shelly is harder than a Sonoff as without an extra clip-on module, they don't have isolated GPIO for a DS18x20. They also don't have many SPCO relay output options.
The simplest automation of a Y-Plan is to replace the SPCO timer switch with an automated relay, and consider bypassing the room themostat. The issue here is what happens if HA crashes? Moving the temperature control down from HA to a microcontroller should increase reliability (less SPOFs), but personally, I'd still add a mechanical frost thermostat.
The room stat is usually distant from the AB valve and tank so comms is needed. Shelly can connect some Zigbee kit directly (not via HA), but you may prefer HA averaging sensors - just consider a HA failure.
Hot water is simpler as sensors are usually next to the tank and AB valve so all local. Be careful if you have a 3kW immersion heater as I'd not personally trust most automated switches at their current rating as the immersion can run continuously leading to heating. This is specifically called out in BS7671, and is why you can plug in a 3kW kettle, but NOT a 3kW immersion.
Shelly has a 25A module that I've used to switch 10A and the terminals look pretty solid.
I replaced my Y-plan with a Honeywell SmartFIT as this had a serial interface and Honeywell dealt with all the complications (hysteresis, cycling limits, etc). If this had died, I may have used a generic ESP8266 module with SPCO relays and DS18x20 as you suggest - but it lasted until an ASHP upgrade became possible.
How water tanks stratify - create water layers at different temperatures, so include more than one port for temp sensors. You can stop heating when just the "top" is warm if water demand is low, but remember it is recommended to heat to 55-60C to prevent Legionella bacteria which can form especially if the tank is not used for a while.
Note that the old "rats nest" choc block "wiring centre" in most UK heating systems can be easily replaced with a much neater box with dedicated Wago connectors.
Yes, you can DIY (I considered this a few times), but unless you are sure of your skills (I am an Electrical Engineer), just buy the convenience of a connected thermostat. Many boilers now include modulation for efficiency so use OpenTherm or a proprietary version that a commercial stat might support. Commercial kit also includes fault detection.
A few folks on the forum have automated Y-plan systems, so search. This DIY automation is not a simple replacement - more a rewire.
If this helps,
this post!