The relevant page is 31 (pdf-page 33), containing a figure "Share of payment instruments broken down into various transaction amount categories in 2014, 2011 and 2008". In particular, 96% of transactions below 5€ were in cash, and 90% for transactions between 5 and 20€.
A breakdown by age group is on page 33. Unsurprisingly, young people pay by card more often than older people.
Various other figure breaking down card/cash usage along different lines are on the subsequent pages. Poorer people use cash for a larger percentage of their transactions than richer people.
Page 63 breaks down usage by occasion/purpose of payment (gas/restaurant/retail/...).
Lastly, 97% of Germans have a girocard (debit card), but only 1 in 3 have a credit card.