Update:
I bought a new ADSL2+ modem (a Netcomm NB6 modem/router, configured in full-bridge mode, i.e. used as a modem only), and substituted it for the Draytek Vigor 2600Plus.
What a contrast! The complete pfSense PPPoE connection and login sequence was successfully completed in under 6 seconds - everything first time. The "power on" to "internet available" time was less than 45 seconds. Now that's more like it. :)
I think that proves beyond reasonable doubt that there's nothing wrong with the pfSense PPPoE client and that my problems were 100% related to interference from the Draytek's PPPoE pass-through mode.