Without getting too technical, the basic difference
between FDMA (Frequency Divided Multiple Access) and TDMA (Time
Divided Multiple Access) is the definition of a channel and how
it is used (accessed). In FDMA a particular bandwidth (E.g. 6.25kHz)
at a particular frequency (E.g. 150.000MHz) is used to define a
channel. Basically, the way channels have been allocated for decades.
In TDMA, the same principle applies regarding bandwidth and frequency,
but the signal is divided into time slots that allow the channel
to have 'extra' capacity in the same bandwidth E.g. Two 6.25kHz
'equivalent' channels in a 12.5kHz channel. See the diagram below
for a graphical explanation.

Until now, TDMA was more spectrum efficient at
wider channel spacing's like 25kHz, as for example, two or three
users could access the same bandwidth as one FDMA channel user.
However, in the case of the newly developed narrowband 6.25kHz
FDMA technology like dPMR, both this and 2-slot 12.5kHz TDMA technology
achieve the same result as far as spectrum efficiency is concerned.