Two goals from bullish front man Reuben Reid, either side of a Ritchie Humphreys' strike, decided the contest, with the visitors controlling possession but unable to transform it into all important goals.
Chesterfield, all in blue, had hardly touched the ball when a cross was headed out only as far as Plymouth midfielder Andres Gurrieri, but his volleyed effort went well over the bar.
Before long the Spireites had their first attack, a well judged through ball finding Marc Richards running towards the byline. He caught up with the ball and tried to cut back to Gary Roberts, but green defenders were on hand to clear away for a corner.
The first ten minutes had been quiet, with newly-crowned League 2 player of the season Gary Roberts combining well with Ollie Banks and suggesting the away side had plenty of spark in their locker.
However, Plymouth striker Reuben Reid had the clearest chance yet when he caught a volley sweetly inside the penalty area. Fortunately for the away fans behind that goal, the shot was straight at ‘keeper Tommy Lee, who was also able to pounce on the rebound in the nick of time.
Starting to put their foot on the ball, midway through the half Spireites midfielder Banks had a pot shot from 30 yards that was saved by a diving Jake Cole in the Pilgrims goal.
Jimmy Ryan was next to try his luck for the visitors from a similar distance. This time the shot took a deflection, but with the sting taken off the shot the ‘keeper was easily able to gather.
Hopes of Chesterfield turning possession into an opening goal were dashed in the 28th minute when Reid was put in on the Chesterfield goal. Beating the offside trap for the first time he controlled his volley across goal and Lee’s fingertips could only divert the ball off the far post but in, giving Plymouth the lead.
Plymouth were suddenly full of confidence, and some nice interplay between Luke Young and Reid allowed Young the space to strike, with his effort sailing harmlessly wide.
Still coming forwards, it was Plymouth’s Reid again at the heart of the action. This time he wriggled past two defenders but with only Lee to beat he pulled a rushed shot wide, much to the relief of the Spireites defence.
Closing in on the interval Chesterfield were finally starting to control things again, and should have equalised after Ritchie Humprheys was brought down for a free kick wide left. Roberts’ free kick was perfect for Ian Evatt, but the defender’s header passed tamely wide when it should have at least tested the ‘keeper.
At the other end it was again Reid causing problems. However, with an open chance to double Plymouth’s lead, he could only shoot over when running on to a cut back, leaving the Pilgrims just a goal ahead at the break.
Out early from the changing rooms, Chesterfield were clearly wanting to impose themselves on the game from the start of the second period. Within three minutes of the restart Marc Richards tested the Pilgrims’ goalkeeper when cutting in from the left, Cole producing a good save to parry away.
It was Richards again who next came agonisingly close to levelling the scores. Tendayi Darikwa drilled in a low cross from the right which the striker stole in on to stab against the crossbar.
The wait for an equaliser was only to be a short one however. A corner was headed out as far as Humphreys who drove a strike back in that deflected off a Plymouth defender and past Cole for his second goal of the season and a vital one for the Spireites.
Barely had Chesterfield restored parity and they were behind again. It was danger man Reid once more who picked the ball up, ran at the defence and rifled home an unstoppable shot from 20 yards.
As in the first half Chesterfield were dominating possession, with the hosts sitting back and ruthlessly breaking. Plymouth forward Tope Obadeyi sprinted past Humphreys wide on the right and bearing down on goal would have scored but for ‘keeper Lee quickly sprinting off his line to make a fine block from the incoming shot.
Substitute Danny Kearns produced some trickery on the wing and a whipped in low cross that beat defenders, goalkeeper and Spireites strikers when a second equaliser seemed likely.
The Spireites, switching to a 4-4-2 with the introduction of another striker in Eoin Doyle, came perilously close to being reduced to ten men when Liam Cooper escaped with a long talking to instead of a second yellow card for a foul just outside the Chesterfield area. From the resulting freekick there was another close shave with Lee holding on to a dangerous headed shot.
Into the final ten minutes and Kearns was in the thick of the action, connecting with a half volley outside the box that produced a brilliant diving save from Cole in the Plymouth goal, Doyle was then flagged offside from the rebound.
Richards was next to test the ‘keeper’s handling, but his well-struck 25 yard shot was central and safely gathered.
Despite the pressure for the away side Plymouth were still creating chances, and could have wrapped up the three points when Conor Hourihane found space eight yards from goal and got a shot away only to see Lee again save with his legs.
Four minutes of extra time were signalled by the fourth official and time quickly ebbed away along with Chesterfield’s hopes, meaning it was Plymouth who secured the win and slowed Chesterfield’s march towards League 2 promotion.