ACR MLG DEVIATED FROM CLRNC ROUTE. NON ADHERENCE TO ATC CLRNC.

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THIS FLT WAS DISPATCHED FROM IAD TO BDL WITH A DPK.DPK 1 ARR. I WAS FLYING THIS ROUTE FOR THE FIRST TIME. THE F/O SAID HE HAD FLOWN THIS ROUTE MANY TIMES IN THE LAST 6 MONTHS. JUST PRIOR TO XING DPK; BOTH VOR'S TUNED TO DPK; I NOTICED THE F/O'S VOR NEEDLE WAS POINTING 40 DEGS TO THE RIGHT AND STEADY. WHEN ASKED WHY; HE SAID; 'BECAUSE WE WERE CLOSE TO THE STATION.' AFTER PASSING DPK AND BOTH VORS TUNED TO MAD; I NOTICED THAT THE #2 VOR NEEDLE WAS POINTING 40 DEGS TO THE RIGHT AGAIN. I ASKED THE F/O AGAIN ABOUT THE DISCREPANCY. HE SAID HIS VOR WAS OK. I LEANED BACK SO I COULD SEE HIS VOR INSTRUMENTS AND SAW THAT HE HAD VOR OFF FLAGS. I BROUGHT THIS TO HIS ATTN. WE WERE 5 MI FROM MAD VOR AND AT THIS TIME BOS CENTER CALLED AND SAID (I UNDERSTOOD) TURN TO A HDG OF 020 DEGS AND INTERCEPT THE MAD 060 DEG R. THE F/O ACKNOWLEDGED. WE WERE IMMEDIATELY ON THE MAD 060 DEG R; WHICH WAS NOT WHAT THE DPK.DPK 1 ARR CALLED FOR. I CALLED CENTER FOR CLARIFICATION AND CENTER REPLIED THAT WE HAD BEEN CLRED TO TURN TO A 020 DEG HDG TO INTERCEPT THE 360 DEG R OF MAD BUT THAT THE VOR WAS 9 MI BEHIND US NOW AND TURN LEFT IMMEDIATELY TO 270 DEGS AND INTERCEPT THE 360 DEG R. PROCEEDED W/O FURTHER INCIDENT. OBSERVATIONS: CAPT SHOULD HAVE BEEN PAYING MORE ATTN TO FLYING AIRPLANE. CAPT HAD LITTLE RECENT EXPERIENCE. F/O HAD 6 MONTHS RECENT EXPERIENCE. CLRNC MISUNDERSTOOD AND NOT READ BACK AS ISSUED BY CENTER; BUT MERELY ACKNOWLEDGED. VERY DIFFICULT TO COM WITH F/O ENTIRE 2 DAYS. HE SEEMED UPSET AND DISTRACTED ABOUT SOMETHING. SOME CONFUSION OVER INOP VOR RECEIVER AND MISUNDERSTOOD CLRNC.