ALTDEV ALT OVERSHOT. THE CAPT WAS BUSY GIVING HIS FO INSTRUCTIONS ABOUT THE DEP WHEN HE MISUNDERSTOOD THE CTLR'S CLRNC AND ORDERED A CLB. THE CTLR INTERVENED AND RECLRED THE ACR.

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TKOF FROM DCA OCCURRED UNEVENTFULLY FROM RWY 36; MOUNT VERNON DEP. APPROX 9-10 DCA DME; ATC ISSUED A CLRNC TO TURN R TO HDG 130 DEGS AND TO CLB. THE FO WAS FLYING THE ACFT. AT THE TIME OF RECEIVING THE CLRNC FROM ATC; I WAS DISCUSSING THE REQUIREMENT TO MAINTAIN A GND TRACK OVER THE POTOMAC RIVER UNTIL 10 DME FROM THE DCA VOR. THE CLRNC I REPEATED TO ATC WAS A 'R TURN TO HDG 130 DEGS AND CLB TO 13000 FT MSL.' UPON PASSING 12000 FT; ATC INSTRUCTED US TO MAINTAIN 12000 FT AS OUR ORIGINAL CLRNC WAS TO 10000 FT MSL. UPON REPEATING THE CLRNC WE LEVELED AT 12000 FT MSL. I THEN INDICATED THAT I RECALLED A REPEATED READBACK OF 'HDG OF 130 DEGS AND CLB TO AND MAINTAIN 13000 FT MSL.' I ALSO INDICATED I READ BACK 13000 FT MSL; BUT RECEIVED NO READBACK OR CONFIRMATION OF THE ORIGINAL CLRNC. I NOW BELIEVE THAT THE DISTR OF DISCUSSING THE VISUAL REQUIREMENT TO TRACK 'UP THE RIVER' AND MY FAILURE TO QUERY THE CTLR REGARDING OUR CLRNC; LED TO THE CONFUSION REGARDING OUR ALT CLRNC LIMIT. IN HINDSIGHT; I BELIEVE THAT AS PIC I SHOULD HAVE FLOWN THE DEP AND NOT RELIED UPON; OR ASSUMED THAT THE FO HAD SIGNIFICANT EXPERIENCE FLYING OUT OF DCA. WE HAD BRIEFLY DISCUSSED RECENT OPERATING EXPERIENCE OUT OF ARPTS CONTAINED ON THIS PARTICULAR TRIP. SECONDLY; CRUISE ALT WOULD HAVE PROBABLY BEEN MORE APPROPRIATE TO HAVE DISCUSSED THE MOUNT VERNON VISUAL DEP FROM RWY 36. LASTLY; I WILL BE MORE AGGRESSIVE IN QUERYING ATC REGARDING CLRNCS ESPECIALLY PERTAINING TO ALT LIMITS.