Ten-man Chesterfield lost out to Notts sub Jorge Grant's looping header on the hour and his last kick of the game free-kick after a foul by Sam Hird, the hosts gaining a man advantage after Scott Wiseman picked up a red card just before the break.
The Spireites had chances but fewer than Notts carved out as they slipped to a third straight season starting defeat.
Ian Evatt returned to the side following his one match-ban - Laurence Maguire made way - whilst Robbie Weir replaced Jak McCourt in the engine room. Gary Caldwell started the game with his side lining up with three at the back plus wing-backs and three in attack.
County included former Spireite Dan Jones at left-back whilst experienced striker Jon Stead, who went into the game with six goals in seven career appearances against Chesterfield, lined up alongside the equally experienced Shola Ameobi.
Chesterfield's last five league visits to Meadow Lane have all featured just a single goal, with three home wins to two always; you have to go back to 1999, when the Magpies won 2-0, to find the last occasion where either side bagged more than one in a points bearing fixture.
With both sides looking for their first points of the season, the game started in bright sunshine with Kristian Dennis whipping in an early cross for ex-County loanee Chris O'Grady, but his header skidded well wide.
County earned the first corner after Joe Anyon failed to hold a ball in from a free-kick but he made amends with a strong punch away from the resulting flag-kick on the right.
Robbie Weir blocked well as Notts enjoyed their first sustained attacking spell and Sam Hird deflected an Ameobi shot for a corner that the rearguard dealt with well. The same player failed to collect cleanly from a fine left wing ball in.
Wiseman tackled well but at the expense of a corner that saw Dennis head away ahead of a counter that saw Dennis have a shot blocked and Louis Reed drive the rebound just wide.
Evatt headed a long throw out for County's fourth corner, O'Grady cleared it and then cleared again from the next throw, starting a break that, off the ball, saw Gozie Ugwu make contact with Elliott Hewitt to pick up a yellow, much to the annoyance of the home contingent.
Reed slipped to allow Ameobi in but Hird mad a fine block for another corner as Notts continue to enjoy the majority of possession and territory, but the set play came to nothing.
O'Grady fed Ugwu but his cross in was cleared and moments later Ugwu was put in behind the County line but keeper Adam Collin won the one-on-one battle from the game's first real opening with 34 minutes played.
Anyon then denied Lewis Alessandra with a diving save and the keeper again had to be alert from the corner to gather in Hewitt's shot. Hird cleared off the line from Yates and from the second phase of the corner, Anyon saved from Stead as County stepped up a gear again.
Hird whipped in a cross that just eluded Ugwu and with half time approaching, for the second weekend in a row, Chesterfield were reduced to ten. Wiseman baulked Hawkridge just outside the box with the ball seemingly destined for Anyon but referee Haines deemed the action to have denied Notts a goalscoring opportunity and the red card was held aloft.
Ugwu escaped a second yellow but had a stiff lecture from the ref after a foul in stoppage time of what was Chesterfield's first 45 minutes of the season without a goal being conceded.
Unsurprisingly, given the yellow card, Ugwu was withdrawn at the break with Maguire coming on.
Within a minute of the restart, Barry found Donohue but he hesitated slightly and saw his right footed shot blocked. Reed was booked for a late challenge on Jones.
Hewitt felled Barry a few from the 30-yard free-kick but Donohue's low delivery didn't fall for Dennis who was the intended recipient. Chesterfield were looking the busier side despite their numerical disadvantage but picking the right final ball was eluding the visitors.
Anyon punched two balls in clear as Notts revived but he was beaten on the hour by a looping header from sub Grant, just seven minutes after his introduction.
Evatt erred on the halfway line and let Stead in but Anyon rescued the situation with a low save and the corner was overhit by County.
Delial Brewster replaced Dennis and almost instantly drove a 20-yarder within inches of the upright and he saw another box- edge effort blocked after O'Grady flicked on and he headed on target, albeit weakly, from a Barry cross.
Anyon denied Hawkridge five minutes from time as Chesterfield went 3-3-3 in a bid to find some reward from the game.
Five minutes of added time saw Reed's free-kick bundled clear but Kevin Nolan's Magpies negotiated the task well and added to their tally right at the end with Grant's 20-yard free kick to register their first points of the season.
Notts: Collin, Tootle (Walker 83), Duffy, Yates, Jones, Alessandra (Grant 53), Hewitt, Brisley, Hawkridge, Stead (Forte 76), Ameobi. Subs (not used): Fitzsimons, Hollis, Hunt, Milsom.
Goals: Grant 60, 90+7
Chesterfield: Anyon, Wiseman, Evatt, Hird, Donohue, Barry, Weir (Mitchell 83), Reed, Dennis (Brewster 73), Ugwu (Maguire 46), O'Grady. Subs (not used): Lee, Sinnott, Wakefield, McCourt.
Referee: Andy Haines (Tyne & Wear)
Bookings: Ugwu, Reed, Weir, Hird (Chesterfield), Grant (Notts)
Sent-off: Wiseman (Chesterfield) 44 mins
Attendance: 7,021 (1,328 from Chesterfield)