Centripetal force is not some additional force like tension, gravity, normal forces, etc. are. It is just a specification of a force component just like how we talk about "horizontal forces" and "vertical forces". Many different forces can be centripetal forces just like how many different forces can be horizontal or vertical. So in the case of a ball attached to a rope spinning in a horizontal circle, there aren't two relevant forces of tension and a centripetal force; the tension force is a centripetal force in this case. This is just like how gravity is a vertical force, or how if you push a box along the floor the force you apply is a horizontal force.
Therefore, let's go over a simpler example first. Let's say you have a rope that can withstand $1\,\rm N$ of force before breaking, and let's pull horizontally on a $1\,\rm{kg}$ box with it. Then of course the rope will break if we try to accelerate the box at $1\,\rm{m/s^2}$ or more. This is because we know that the horizontal force component by Newton's second law is $F_h=ma_h=T$. Notice how there is just one relevant force here: tension. We haven't said there is a tension force and a horizontal force, as tension force is a/the horizontal force in this case.
Now let's take the same rope and same box and spin the box in a horizontal circle of $1\,\rm m$. Now the tension force is a centripetal force. Since we know from Newton's second law that the magnitude of the centripetal force is $F_c=ma_c=mv^2/r=T$, this means that largest speed we can move the box at is $1\,\rm{m/s}$ before the rope breaks. Notice how there is just one relevant force here: tension. We haven't said there is a tension force and a centripetal force, as tension force is a/the centripetal force in this case.
With all of this in mind, let's address specific parts of your question:
why is it that when a ball spinning on a rope has a centripetal force larger than the tension of the rope...
For horizontal circles this is not possible because the tension force is the centripetal force responsible for the circular motion. For vertical circles gravity also has a centripetal component depending on where the object is in the circle, but even then the better wording would be "the rope breaks when its tension force would need to be larger than its maximum amount to produce the required acceleration".
...is it not the centripetal force what keeps it going in a circle and so it will continue going in a circle since there is still a centripetal force, just larger?
If an object is undergoing circular motion then it must have a force acting on it in the centripetal direction, but the centripetal force is just a component label, it's not an additional force. If the force in the centripetal direction goes away then you no longer have circular motion.
has it got something to do with the centrifugal force that the tension can no longer balance and so the ball goes off?
No. If you are viewing the system from an inertial frame of reference then there is no centrifugal force acting on the ball. If the circle is horizontal just the tension force is relevant for the circle. However...
but my understanding is that the centrifugal force is fictitious so cannot be used in an argument.
It is fictitious, but that doesn't mean you can't use it. You just have to understand when you can use it. If you were looking at the scenario in a rotating frame that spins with the ball then you would see a centrifugal force that is equal and opposite to the tension force. But you have to bring the centrifugal force in because you are no longer in an inertial frame reference, yet you still want Newton's second law to be true (at the expense of Newton's third law). If this seems confusing, then you can understand why introductory physics teachers tend to just say "centrifugal forces aren't real, so don't talk about them." :)