If users are frustrated with the old system, and the new system addresses most/all of their pain points, they will generally accept the switch without any complaint, even if they need to learn a new interface.
If people are happy with the old system, there will always be those who want to stick with it, no matter how much "better" the new system is. To reduce the size of this group and the amount of trouble it causes you, you must make it as easy as possible for someone to learn how to use the system - you may want to provide detailed instructions, video tutorials and the like - and of course, strive to make the new interface as intuitive as possible.