Most of mine are with Petplan Equine with a low death of animal value as I've got too many to have accurate market value or loss of use on anything except one of them.
All insurance companies will only pay out on death of animal within very strict BEVA immediate destruction on humane grounds guidelines but Petplan in my experience offer flexible coverage, you can choose exactly what you need whether mostly just vets fees, loss of use, 3rd party liability, tack cover etc. If you've got BHS or other similar membership you'll usually find you already have 3rd party liability cover.
They do seem to pay out (as long as the claim is within their policy rules) without any undue problem - but you cannot ever get through to the people actually handling the claim, however the (mostly) ladies in the Equine section are good at raising queries on your behalf and providing an answer. They were unclear on what additional paperwork they wanted on one of my last claims for a yearling (operation + 2 weeks in hospital for a kick wound) but once I established exactly what it was and got it from the right vet they did pay out. Good job the hospital were very nice about waiting to be paid :-o! Their SLA to respond to emails is not good - 10 days (!!) so I don't bother emailing them anymore, just raise telephone queries through the Equine section.
My vets have also mentioned there is one notorious two lettered company that just will not pay out and should be steered very clear of