gamma-ray spectrum vs energy decay
I will first focus on the 214Bi decay. The 3.272 MeV is the total amount available for the &beta;- decay, i.e. the difference between the ground states of 214Bi and 214Po. If you have a beta decay into the ground state of of 214Po, which happens in 19.9 % of cases (all data are from Firestone, R. B. et al., “Table of Isotopes”, 8th ed., 1998, p. 9211, in short “ToI”), there will be no gamma emission from 214Po, the 3.272 MeV are distributed between the electron and the electron antineutrino. However, in 16.9 % of cases, the decay leads to an excited state of 214Po with an energy of 1764.499 keV which can then deexcite among other possibilities by emission of a 1764.494 keV gamma photon (15.36 % of beta decays). The decay can produce a large number of gamma ray lines, but most happen with low probability. You can have a look at page 23 of this 214Bi table of radionuclides extract to get an impression.

In summary, the 3.272 MeV get distributed in varying proportion to the electron and the electron antineutrino from the beta decay, zero or more gamma-ray photons, and some small amount to nuclear recoil, etc.

In the case of 40K decaying via electron capture to 40Ar (10.72 % of cases), the total decay energy (Q-value) is 1504.9 keV. Most of the time (10.67 %), this goes to an excited state (1460.859 keV), which in turn gives rise to the 1460.830 keV gamma-ray line. The rest of the energy goes to the electron neutrino.

Similarly, for 208Tl, the 5000.9 keV is the Q-value of the &beta;--decay. Most of the time (48.7 %), the decay proceeds via an excited state (3197.743 keV) of 208Pb, which deexcites via another excited state (2614.551 keV) where 99 % of decays also lead. This state the deexcites via the emission of a 2614.533 keV gamma ray photon. I believe the 2.82 MeV from Fig. 15.1 is a typo, since the reference in Reynolds’ book points to the article “Airborne Gamma-Ray Spectrometry Surveys”. There Fig. 4.4-1 is the same as Fig. 15.1 from the book, but in rather low resolution and with hard-to-read numbers. The text, however discusses the 2.62 MeV gamma ray line, which is very likely a rounded value of the 2614.533 keV from the “Table of Isotopes”.

The sum of the probabilities of different gamma ray lines from the same decay can be larger than 100 % if the deexcitation happens via a gamma-ray cascade, i.e. if the nucleus first transitions into an intermediate excited state and then again to the ground state or further intermediate states. This means that a single beta decay results in multiple gamma-ray emissions. This is illustrated in the Wikipedia article on Gamma rays using the example of the 60Co decay which results in two photons emitted in > 99.9 % of cases.