On a PRI, there is something called "virtual groups" that the Telco can program to restrict the number of simultaneous calls for any given number even though you have 23 channels to use. They are employed (when requested) to make sure there are talk paths available for other inbound or outbound calls. You don't run into it very often, but they do exist. Problem is, a lot of CO techs don't even know what they are or how they're used. Your symptoms sound like this is exactly what's happening. If that group is set to only 1 call for that number, that's all you'll get no matter how many idle channels there are on the PRI or how the BCM is programmed. They will send a busy to the caller too.
I once had a number that wouldn't ring in no matter what we did. Problem turned out to be the telco had one virtual group forwarded to another one and it never did hit the pbx even though they insisted they were sending the calls. I argued with the CO for over a week who kept saying they were sending the calls and it was not their problem. Only an escallation up two levels finally got someone who figured it out. Never did get an apology from that guy either!!!!!!!!