Hi,
1) yes, RXFIFO and MBs can be used simultaneously. If RXFIFO is enabled, first 8 MBs are used by RXFIFO engine, rest of MBs can be used for TX or RX operation. This assumes default config for filter elements, if more elements is used in filter table then number of MBs available MBs decreases, see CTRL2[RFFN] for more info.
In past I posted some example https://community.nxp.com/t5/S32K-Knowledge-Base/Example-S32K144-FlexCAN-RXFIFO-DMA-S32DS-ARM-2018-R...
2) there is no HW support for triggering TX messages. You can fill MB by DMA upon SW request, if MB is written backward, from last payload word to CS word, it can probably work too. But the question is if there is any benefit for this kind of operation
BR, Petr