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I would like to know if there is any...

Exactly that is what you should check, if there is any of the elements in the block which is true:

receive_payment_on = config[:sections].any? do |section|
  if section[:applicants]
    section[:applicants][:sections].any? do |app_sec|
      app_sec[:employment] && app_sec[:employment][:receive_payment_on]
    end
  end
end

In Ruby (or any language with functional capabilities, for that matter) it's not idiomatic to use a imperative loop to do that.