In order for a Price Scheme to apply, you need to have both the account or job role if both are specified in the scheme itself.
For example, if you have the combination shown below of account and user type, for this price scheme to apply, you would have to meet both of the criteria for this to apply.
Meeting the account or the job role on their own would not work.
See this ticket https://accessplanit.atlassian.net/jira/servicedesk/projects/HLP/queues/custom/17/HLP-27458 for an example of this.