The other fresh appointee is Jamie Booth, who was part of Jarrold's sales team at Southernprint, prior to joining Stibo Group last year.
Both will report to group sales director Andrew Clay, tasked with developing strategic relationships at key clients with requirements that span the £387m-turnover group's service offering.
Jarrold is known to have received various approaches since he left Southernprint last August, following its acquisition by Walstead Investments. He described the opportunity at St Ives as "fantastic".
"When I look at the sector, there are actually only one or two companies in a good position to take it forward," he said. "St Ives is financially strong, with a great reputation and a great range of services that can help customers be more successful."
Booth joins the group next Monday (15 February), while Jarrold will take up his new role at the beginning of March.