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I don’t think extra politeness is going to help you much here. If you don’t do what they ask you to do and they don’t understand why, they’ll probably assume you’re being rude, no matter which words or tone you choose.
You don’t need to explain yourself. Others need to learn to respect your choices about yourself. Yes, it’s tiring. It’s their fault, but partly your problem.
Your responsibility ends with “Thank you, but no.” Unfortunately, some people will feel hurt by this, no matter how cheerily you say it, because they simply don’t expect it. They will tell themselves that you are not being genuine by trying to both remain friendly and deny their request. You can’t change this; only they can choose to interpret your response differently. And most people never try this. Instead they merely expect you to be agreeable and do what they want you to do.
If you want to establish your boundaries, then you need to practise letting them feel hurt and not feeling responsible for it. This is one reason I meditate.
Peace.
You failed just now, so why would someone take your opinion about this seriously? (If this bothers you, then try reading it again in a cheerier tone. Oh! That didn’t help? Strange.)