Practice!
When you're alone, practice saying "No" in various ways, from polite to "what part of 'no' don't you understand?" Eventually, the phrases will flow out quite naturally.
The proper mindset is key as well. Keep telling yourself that you have just as much right as the next person to be respected and heard. It may be a case of "fake it 'til you make it" but keep doing it. Your self talk can influence how you react to situations.
Know that your confident. no one will respect you until you respect yourself. Just know that your the pilot of your own life and learning to say "no" is as easy as learning to say "yes". i hope i helped!
Assertivness is not about being rude. It seems like you (as I used to do the same) feel you need to explain why you are saying no, you don't have to! You need to be able to say no without having to give a reason but just repeat yourself eg: You :'No, I'm sorry, I can't'
Them: 'But why?
You: 'I just can't do it .'
Them: 'Why?'
You: : 'I just can't and I really don't need to give a reason, I just can't do it'
Them: 'But why not?'
You: 'I won't be doing it, maybe you should ask someone else'
You may notice that if anyone has ever asked you if you can do something for them and you say no then they keep on and on, you need to keep on and on by just saying no, without an attitude, just a 'no I can't'
Next time someone catches you off guard, just say...I will get back to you as I am unsure if I can help you, that will give you some time to pluck up the courage you may need, then give them a call a day later and say...I am sorry but I cant help
watch what you say and the tone of your voice you don`t wanna to start off wrong because it will end up into a conflict and maybe the situation could get worse and also say how you feel honestly and if the person doesn`t cope with that then that`s their problem not yours and the next time they do something say whats on your mind with out holding back that means your tone and everything just let it out
Have confidence in what you believe in and in yourself, and don't worry about what other people think. You know who you are are what your standards are, and if you don't want to do something then say no! Don't lower yourself to what other people want you to be. You may lose some friends along the way, but if they were truely your friends.. they would't have stopped being your friend from you saying no! =] Just follow your heart and God will help you through anything.