There are technique used in time-resolved fluorescence(or emission) spectroscopy. You can get or draw a decay curve directly from the emission spectra(intensity Vs wavelength plot).
In order to measure a decay plot, you'll need a time-correlated system in which you monitor an emission wavelength and its intensity over time (usually ns to ms) (i.e. TCSPC).
You cannot get a decay curve just from a steady state emission spectrum. But if you had recorded the emission spectrum as a function of time at different time intervals then it would be possible.
Record emission spectrum decaying as a function of time (plot of fluorescence intensity vs wavelength). [This can be done using a fast CCD . But there are limitations in terms of the fluorescence lifetime one can measure]. Then decay curve can be obtained just by selecting fluorescence intensity at a single wavelength and plotting intensity as a function of time will give you the decay curve.This can be done at other wavelengths too.