With open center hydraulics you can't tee off a pressure line. With open center, there is constant flow from the pump. It flows through each valve in turn, then to the 3pt and into the tank. When you operate a valve the flow is diverted, into cylinders or whatever is attached to the valve. It gets a little more complex in that there are two types of valve, one that has just an in and an out in addition to work ports to operate cylinders, and one that has an in, power beyond and tank. Either kind can support other valves after them in the chain (though there are caveats that I'm leaving out to keep it simple). The key thing to remember is that when you operate a valve, it pressurizes the entire chain before it. So they need to be designed for that.
When you put the backhoe on and plug it in, you're just adding it's valve stack to the chain.
You can add a thumb in a few ways. You can put a new valve for it in the stack on the BH. That's the cleanest. You can use a diverter to divert the flow from another BH valve like stabilizer, to the thumb. That can be electric or mechanical. Or you can plumb the thumb in to the tractor. That's when the caveats come in. Many BH valve stacks are not designed to be pressurized by valves farther down in the chain, which is why you're not supposed to operate the 3pt with the BH connected. If you connect the thumb before the BH in the chain, then its valve needs to be able to handle full pressure when the BH is operated. Also, if the thumb is connected before the BH, using it will keep the BH from getting (much) flow, so you won't be able to move the thumb and BH at the same time.