The more strings to your bow the better David. Payroll is a good idea and one of the bookkeeping associations offers a Self Assessment exam. Both these are tie-ins to clients that you will likely be seeking. So if they're happy with the bookkeeping, you can offer services which are actually easier if you're already familiar with the business. With SA tax returns, there may be family or friends that you can offer to complete or at least check. You can do this online with HMRC's free software to begin with.
I like Tim would suggest the Level III Diploma in Self Assessment Tax Returns, however, do any of your existing clients require Payroll, or are any of them Limited or changing to Limited?
I would have thought most of your clients would require the self assessment, so this would be an extra service you could offer to current clients, much easier than getting new clients.
Also it might help you do your own, if you don't already.
Otherwise it tends to depend on what your existing clients, or potential clients, are asking for. Do you have clients who are limited and might be happy for you to take their accounts further? Most limited companies will require Payroll so perhaps do the Level III first, then Payroll, to get the Limited companies as clients, then add the additional payroll service later.
I would like to say thank you very much for your advice and suggestions. I have now made a decision and I will be doing the Level III Diploma in Self Assessment Tax Returns in the near future.
Thank you again to everyone, I much appreciate it.