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Block via .htaccess or The Shield Plugin ?
It depends. If you want to block a few IPs or range of IPs, i guess .htaccess method is best. Best because it is "closer" to the webserver and doesn't involve any Wordpress/PHP/Database.
But if you want something to dynamically block unwanted visitors (spammers, hackers, bots etc etc), then The Shield plugin for Wordpress may work better. You can block for an hour, a day or a week max, and if the visitors comes again within that time, the timer is reset and the block starts again from the beginning.
I was using a WEEK for ban time, but that was a lot and the IP check was slowing down the site. So i'm now using blocking for a DAY and that seems to work just fine.
But all the above depend also on your hosting server and plan resources.