Finally solved problem of not being able to send e-mail from my Nokia Lumia 630 (POP/SMTP account) using WiFi. Seems every WiFi service provider has its own outgoing email server so one needs to set this up correctly. For folks with a similar problem, try the following as it worked for me. Go to All Settings & tap 'email+accounts'. Delete problematic email account (tap & hold). Tap 'add an account'. Select 'other account'. Set up the account as before but under advanced settings, insert the name of the outgoing (SMTP) email server provided by the specific WiFi host service being used (usually this info is available on the Internet webpage of the host provider or by phone). Usually no authentication is required. Alternatively (and this worked for me) set the outgoing (SMTP) email server exactly the same as the incoming server (in my case 'pop3.telkomsa.net') and check 'outgoing server requires authentication'. Usually no SSL is required.
If you are not using WiFi but rather a data connection (All Settings, 'mobile + SIM', set 'data connection' on), then the outgoing email server needs to be set to that provided by your SIM card provider, in my case MTN, which is 'mail.mtn.co.za'.