I've looked into this and it seems like there is no software out there that makes this easy. For it to be convenient enough to make sense, I think there would have to be some router 'login' page which makes downloading and installing the certificate as easy as possible. But, even 'easy as possible' would probably be too inconvenient for any guests who just want to use your wifi. Maybe it could be optional somehow. Don't install the custom certificate? Fine but you'll still get ads. Install the custom certificate? Awesome, your ads will be blocked.
Back then you could simply block ad.youtube.com and there would be no ads but today Google is serving ads via their main domain. You can't block ads unless you block youtube.com.
So now no DNS based adblocker can block YouTube ads. uBlock is the only option which works inside browser only.
Without being able to read the destination IP address, all the middlemen between your device and your destination server, wouldn't know where to forward your request. Your request would never make it to its destination website. The destination IP address is retrieved when you access a website. When you type google.com into the address bar, your computer sends out something called a DNS request to something called a DNS server. That DNS server sends back the destination IP address for the website you're trying to access. This DNS request is unencrypted and so PiHole can simply intercept it before it leaves your network, check if it's an ad domain, and if it is an ad domain, send back trash data to your device instead. Your device, unable to retrieve the destination IP address, is now blocked from accessing that content.
To prevent people from being able to block their ads via DNS, Google hosts ads on domains which are critical to using their services. For example, YouTube ads might come from youtube.com. This way, if you block YouTube ads using PiHole, you are also blocking the entire YouTube service as well.
UBlock Origin and other browser-based adblocking tools are able to block with a more fine-grained approach because they live in your browser and don't have to worry about SSL.
PiHole works at the DNS level, it can't block things if they're served from the same domain
I think you should install both though. Pihole can block ads on apps, and can block CNAME cloaking.