Try this:
(lldb) break set -n main
(lldb) r
(lldb) thread backtrace
frame #0: 0x0000000000405696 app`main(argc=1, argv=...) + 22 at app.cpp:11
frame #1: 0x00007ffff7216ec5 libc.so.6`__libc_start_main + 245
frame #2: 0x0000000000401f79 app
The frame below (before) main is the one you want, and it's showing the library and function name. You can set a breakpoint on it just like any other:
(lldb) break set -n __libc_start_main
Breakpoint 1: where = libc.so.6`__libc_start_main, address = 0x00007ffff7216dd0
or, to be more specific:
(lldb) break set -s libc.so.6 -n __libc_start_main
Breakpoint 2: where = libc.so.6`__libc_start_main, address = 0x00007ffff7216dd0
If you know the address, you could use it directly:
(lldb) break set -a 0x000000...
Then restart the process, and you should hit it immediately:
(lldb) r
There is a running process, kill it and restart?: [Y/n] y
...
* thread #1: ...__libc_start_main, name = 'app', stop reason = breakpoint
frame #0: 0x00007ffff7216dd0 libc.so.6`__libc_start_main
-> ...: pushq %r14
(lldb)