Send E-mail smart service not sending to the second email recipient

That's not a valid expression. If you want to create a list, use curly brackets and a comma as the separator.

{
  toemailaddress(
    pv!spkrRecord['recordType!PMSO Speaker.fields.speakerEmail']
  ),
  toemailaddress(
    pv!parishProfileRecord['recordType!PMSO Parish Profile.fields.parishContactEmail']
  )
}

That worked.  So much for trying to follow the documentation!!  Follow the experts!!!

Configuring the email recipients can be a bit confusing. Directly in the dialog, Appian shows multiple addresses with a semicolon separator. But when you add more using the script editor popup, you will have to follow the normal Appian scripting syntax.

And, when we are already talking about this dialog. When you enter something in the scripting popup, this is always ADDED to the list of addresses in the recipients field. To replace any existing addresses, you need to clean up the field first.

Configuring the email recipients can be a bit confusing. Directly in the dialog, Appian shows multiple addresses with a semicolon separator. But when you add more using the script editor popup, you will have to follow the normal Appian scripting syntax.

And, when we are already talking about this dialog. When you enter something in the scripting popup, this is always ADDED to the list of addresses in the recipients field. To replace any existing addresses, you need to clean up the field first.