During a first half where Tom Leak rattled the crossbar for United, the hosts scored three times through a Jimmy Knowles brace and Keaton Ward's brilliant effort.
Aaron Martin reduced the arrears for the visitors nine minutes after half-time, but the Pilgrims managed the second half well to claim their first victory of the campaign.
United, sporting an unchanged XI from their 1-1 opening day draw at Buxton, went close to a carbon copy of their leveller at Silverlands - with Kelsey Mooney heading narrowly over the bar following Zak Mills' cross from the right.
The Pilgrims edged in front on the 20-minute mark when KNOWLES worked some space outside the box and blasted home a low effort from 20 yards to leave keeper Myles Boney flat-footed.
Leak thundered Martin Woods' corner against the crossbar, but United were soon two goals to the good when Tom Broadbent underhit a backpass to Boney and KNOWLES nipped in to walk home his and Boston's second.
United saved the best until last when WARD sent a dipping volley into the far corner of Boney's net after meeting Keziah Martin's throughball with real aplomb.
Shields responded after the break and cut the deficit in the 54th minute when MARTIN headed John Lufudu's cross back where it came from to get the visitors on the scoresheet.
Cameron Gregory subsequently made a fine save to deny Jed Abbey as Shields threatened to mount a serious comeback - but once a further Martin header dropped wide from an Abbey cross, the visitors' assault was contained well by a determined United side.
Boston (4-1-2-1-2): Cameron Gregory; Zak Mills, Michael Bostwick, Tom Leak, Brad Nicholson; Martin Woods; Jordan Richards, Keziah Martin; Keaton Ward (Sam McLintock 74); Kelsey Mooney (Michael Gyasi 85), Jimmy Knowles (Oliver Wilson 85). Subs (not used): Tom Edge, Tyler Knowles.
South Shields (4-1-2-1-2): Myles Boney; John Lufudu, Gary Liddle, Tom Broadbent, Blair Adams; Rob Briggs (Joao Gomes 84); Lirak Hasani, Jed Abbey; Mackenzie Heaney (Luke James 69); Aaron Martin (Jordy Mongoy 90), Paul Blackett. Subs (not used): Dillon Morse, Martin Smith.
Referee: Harry Jones.
Attendance: 1,678 (155 visitors).
PIC: Tim Hoff.