The solution provided here can, of course, be expanded and customized with different designs. The key is to understand and convey the underlying logic. First, a request form is designed on the Customer Portal as follows:
Next, if the user selected as the "Coverer" meets the necessary criteria while the issue is in the approval status, they are added to the "Approvers" field using a rule like the one below:
lookupIssues:
"Request Type" = "Out of office request (IT)" AND statusCategory != Done AND "Start date[Date]" <= startOfDay() AND duedate >= now() AND reporter ="{{issue.customfield_10003}}"
P.S: In this case, {{issue.customfield_10003}} is User field - Actually, the real name of this field is User, but I've listed it as Coverer Approver on the portal side. It needs to be the same field as the User in {{lookupIssues.User}}, which is the last step in the automation process.